JP2020533423A - Silicone Polyether Copolymers, Sealants Containing It, and Related Methods - Google Patents

Abstract

Silicone polyether copolymers have the formula Xg [ZjYo] c, where each X is an independently selected silicone moiety having a particular structure, and each Y is independently selected. It is a polyether moiety, each Z is an independently selected siloxane moiety, the subscript c is 1-150, the subscript g is> 1, and is indicated by the subscript c. The subscripts j and o are independently> 0 and <2, provided that j + o = 2 in each part. Methods for preparing silicone polyether copolymers are also disclosed, including reacting a polyether compound, a chain-extending organic silicone compound, and a terminal-protected organic silicone compound in the presence of a hydrosilylation catalyst. Sealants are also disclosed, which include silicone polyether copolymers and condensation reaction catalysts. [Selection diagram] None

Description

Cross-reference to related applications This application has priority over US Provisional Applications 62 / 524,637, 62 / 524,636, and 62 / 524,639 filed June 26, 2017. All advantages are claimed and these contents are incorporated herein by reference.

The present invention generally relates to copolymers, and more specifically to silicone polyether copolymers, methods of preparing them, and sealants containing them.

Sealants are known in the art and are used in numerous end-use applications and environments. The physical and performance properties of the sealant, as well as the particular curing mechanism associated therewith, are generally selected based on the particular end application and environment in which the sealant is utilized. Sealants can be based on a variety of different chemical properties and curing mechanisms. For example, the sealant is silicone-based and can include organopolysiloxanes. Alternatively, the sealant may be organic and may contain organic components, for example to form urethane. Hybrid materials are increasingly being used for sealants, allowing them to combine the benefits traditionally associated with silicone-based sealants and organic sealants.

For example, silane-modified polyethers are increasingly being used in sealants as hybrid materials. However, existing silane-modified polyethers have limitations. For example, conventional sealants containing silane-modified polyethers have an undesired cure rate. In addition, such sealants are less thermally stable than those without hybrid materials and can undergo unintended side reactions before or during curing.

A silicone polyether copolymer having the formula X _g [Z _{j Yo} ] _c is disclosed. Each X is an independent silicone moiety having one of formulas (I) or (II).
Each Y is an independently selected polyether moiety and each Z is an independently selected siloxane moiety having the formula [R ¹ _h SiO _{(4-h) / 2} ] _d . In these moieties, each R ¹ is an independently selected substituted or unsubstituted hydrocarbyl group with 1-18 carbon atoms and each R ² is an independent with 1-18 carbon atoms. Each D ¹ is an independently selected divalent hydrocarbon group having 2 to 18 carbon atoms, and each subscript a is independent. 0 or 1, each subscript b is independently 0 or 1, subscript c is 1-150, each subscript d is 1-1000, and each. The subscript e is independently 1 or 2, and each subscript f is independently 0 or 1 provided that b is 1 if f is 1 in each X. , The subscript g is> 1, the subscript h is independently selected from 0-2 of each part indicated by the subscript d, and each subscript j is independently> 0. And <2, and each subscript o is independently> 0 and <2, and the subscript t is ≧, provided that j + o = 2 in each part indicated by the subscript c. It is 0 and the subscript u is> 0.

A method for preparing a silicone polyether copolymer is disclosed. In this method, a polyether compound having two or more terminal unsaturated groups on average, a chain-extending organic silicone compound, and a terminal-protected organic silicone compound are reacted in the presence of a hydrosilylation catalyst to form a silicone polyether. Includes obtaining copolymers.

The sealant is also disclosed. The sealant contains a condensation reaction catalyst and further contains a silicone polyether copolymer.

Cured products are also disclosed. The cured product is formed from the sealant. In addition, composite articles and methods of adjusting composite articles are disclosed. The composite article comprises a substrate and a cured product placed on the substrate. The method comprises placing the sealant on a substrate and curing the sealant to feed the cured product onto the substrate, thereby preparing a composite article.

Silicone polyether copolymers have the formula X _g [Z _{j Yo} ] _c , where each X is an independent silicone moiety having one of formulas (I) or (II).
Each Y is an independently selected polyether moiety, and each Z is an independently selected siloxane moiety having the formula [R ¹ _h SiO _{(4-h) / 2} ] _d , in the formula. , Each R ¹ is an independently selected substituted or unsubstituted hydrocarbyl group having 1-18 carbon atoms and each R ² is independently selected having 1-18 carbon atoms. Subscripted or unsubstituted hydrocarbyl groups, each D ¹ is an independently selected divalent hydrocarbon group having 2 to 18 carbon atoms, and each subscript a is independently 0 or 0 or 1, each subscript b is independently 0 or 1, subscript c is 1-150, each subscript d is 1-1000, each subscript e Is 1 or 2 independently, and each subscript f is independently 0 or 1 and the subscript character, provided that b is 1 if f is 1 in each X. h is independently selected from 0-2 of each part represented by the subscript d, and each subscript j is independently> 0 and <2, and each part represented by the subscript c. Under the condition that j + o = 2, each subscript o is independently> 0 and <2, the subscript t is ≧ 0, and the subscript u is> 0.

Each R ¹ and each R ² are independently selected and can be linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups as well as saturated or non-conjugated cyclic groups. The cyclic hydrocarbyl group can be monocyclic or polycyclic. Linear and branched hydrocarbyl groups can be independently saturated or unsaturated. An example of a combination of a linear and cyclic hydrocarbyl group is an aralkyl group. "Substitution" means that one or more hydrogen atoms can be replaced by atoms other than hydrogen (eg, halogen atoms such as chlorine, fluorine, bromine), or carbon atoms in the chain of R ¹ and / or R ^2. Means that can be replaced by an atom other than carbon, that is, R ¹ and / or R ² can contain one or more heteroatoms in a chain such as oxygen, sulfur, nitrogen. Suitable alkyl groups are methyl, ethyl, propyl (eg, iso-propyl and / or n-propyl), butyl (eg, isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (eg, sec-butyl). , Isopentyl, neopentyl, and / or tert-pentyl), hexyl, and branched saturated hydrocarbon groups of 6 carbon atoms, but are not limited thereto. Suitable aryl groups are exemplified by, but not limited to, phenyl group, tolyl group, xsilyl group, naphthyl group, benzyl group, and dimethylphenyl group. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Suitable monovalent halogenated hydrocarbon groups include, but are not limited to, alkyl halide groups having 1 to 6 carbon atoms or aryl halide groups having 6 to 10 carbon atoms. Suitable alkyl halide groups are exemplified by, but not limited to, the above alkyl groups in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl. For example, fluoromethyl group, 2-fluoropropyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 4,4,4,3,3-pentafluorobutyl group, 5 , 5,5,4,5,4,3,3-heptafluoropentyl group, 6,6,6,5,5,4,5,4,3,3-nonafluorohexyl group, and 8,8,8,7, 7-Pentafluorooctyl group, 2,2-difluorocyclopropyl group, 2,3-difluorocyclobutyl group, 3,4-difluorocyclohexyl group, and 3,4-difluoro-5-methylcycloheptyl group, chloromethyl group. , Chloropropyl group, 2-dichlorocyclopropyl group, and 2,3-dichlorocyclopentyl group are examples of suitable alkyl halide groups. Suitable aryl halide groups are exemplified by, but not limited to, the above aryl groups in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl. For example, chlorobenzyl and fluorobenzyl are suitable aryl halide groups.

In certain embodiments, each of R ¹ and R ² is an independently selected alkyl group. In certain embodiments, R ¹ and R ² are different from each other. For example, in these embodiments, R ² may contain more carbon atoms than R ¹ . In certain embodiments, each R ¹ is methyl and each R ² is propyl.

Respect silicone polyether copolymers, partial formula [Z _j Y _{o] c} is to be understood that it is not intended to mean a straight-chain structure of the copolymer moiety represented by ZY. Rather, as is understood in the art, the copolymer ZY can be linear or branched, with each moiety indicated by the subscript c being independently selected. Thus, the silicone polyether copolymer comprises a number of c in the copolymer moiety ZY, each containing a number of o in the polyether moiety Y and a number of j in the siloxane moiety Z. In addition, as will be understood in light of the following description, each polyether portion Y and siloxane portion Z will be independently selected both within and between such portions, as indicated by the subscript c. , And each can be linear or branched.

Each subscript c is 1 to 150, such as 1 to 100, 1 to 50 alternatives, 1 to 25 alternatives, 1 to 10 alternatives, 1 to 5 alternatives, and so on. The subscript g is 1.1-10, alternative 1.1-8, alternative 1.1-6, alternative 1.1-4, alternative 1.1-3, alternative 1.1 to 2, alternative 1.1 to 1.9, alternative 1.2 to 1.8, alternative 1.2 to 1.7, alternative 1.3 to 1.7 , Alternatively 1.4 to 1.7, alternative to about 1.4, 1.5, 1.6, or 1.7, etc., greater than one. Each subscript j is> 0 and <2, and each subscript o is> 0 and <2, provided that j + o = 2 in each portion indicated by the subscript c. Therefore, the subscripts j and o can be considered as mole fractions, for example, j = 1 and o = 1 of the siloxane portion Z and the polyether portion Y of the portion indicated by the subscript c. Equal to a 0.5: 0.5 molar ratio. Of course, the molar ratio of Z to Y for each part indicated by the subscript c is limited only by the requirement that both the siloxane part Z and the polyether part Y be present in each part indicated by the subscript c. Will be done. For example, the Z: Y molar ratio is independently about 1000: 1 to about 1: 1000, alternatives about 100: 1 to about 1: 100, and alternatives in each portion indicated by the subscript c. It can be about 10: 1 to about 1:10, alternatives from about 5: 1 to about 1: 5, and alternatives from about 2: 1 to about 1: 2. As described above, partial formula [Z _j Y _{o] c} is not intended to mean a straight-chain structure of the copolymer moiety represented by ZY. Similarly, the partial formula does not require the specific structure of any of the copolymer partial ZYs. Rather, depending on the values selected for the subscripts j and o, the copolymer moiety represented by the partial formula [ZjYo] c may be in block form (eg, ZZ, YZ, YZ-Y). , Z-Y-Z-Y, YY-ZZ, etc.) or may include random forms of the siloxane moiety Z and the polyether moiety Y. In certain embodiments, the silicone polyether copolymer comprises a 2: 1 ratio of a polyether moiety Y and a siloxane moiety Z. In some such embodiments, the polyether moiety Y and siloxane moiety Z, such that the silicone polyether copolymer having the formula X _{g Y} [ZY] _c, present in the silicone polyether copolymers in block form, The subscripts c and g are defined above. In some of these embodiments, the silicone polyether copolymer comprises a linear polyether moiety Y and linear siloxane moiety Z, silicone polyether copolymer the _{"formula X g 'Y [ZY] c} X g Each of g'and g'is terminally protected by a silicone moiety X to have, in which c is defined above and g'+ g'is> 1. ≧ 0.

In general, for each X, each subscript a is independently 0 or 1. Generally, the subscript a is 0. In some embodiments, each subscript a is 0. In certain embodiments, the silicone polyether copolymer comprises at least one X with the subscript a of 1.

For each X in formula (I), each subscript b is independently 0 or 1. In some embodiments, each subscript b is zero. In other embodiments, each subscript b is 1. In a further embodiment, the silicone polyether copolymer comprises at least one X of formula (I) with the subscript b of 0 and at least one X of the formula (I) with the subscript b of 1. ,including. Each subscript e is independently 1 or 2. In some embodiments, each subscript e is 1. In other embodiments, each subscript e is 2. In a further embodiment, the silicone polyether copolymer comprises at least one X of formula (I) with the subscript e of 1 and at least one X of the formula (I) with the subscript e of 2. ,including. Each subscript f is independently 0 or 1 provided that b is 1 when f is 1 in each X. In some embodiments, each subscript f is zero. In other embodiments, each subscript f is 1, so each b is 1. In a further embodiment, the silicone polyether copolymer has at least one X of formula (I) where the subscript f is 0 and the formula (I) where the subscript f is 1 and b is 1. I) includes at least one X and.

For each X in formula (II), the subscript t is ≧ 0. In certain embodiments, the subscript t is 1-100, such as 0-80, alternative 0-60, alternative 0-30, alternative 0-10, alternative 0-5, and so on. is there. The subscript u is> 0. In certain embodiments, the subscript u is 1-20, such as 1-15, 1-10 alternatives, 1-7 alternatives, 1-5 alternatives, 1-3 alternatives, and so on. is there.

Each D ¹ has 2 to 18 carbon atoms, 2 to 16 carbon atoms in the alternative, 2 to 14 carbon atoms in the alternative, 2 to 12 carbon atoms in the alternative, 2 in the alternative. 10 to 10 carbon atoms, 2 to 8 carbon atoms to replace, 2 to 6 carbon atoms to replace, 2 to 4 carbon atoms to replace, 2 or 3 carbon atoms to replace Alternatively, it is an independently selected divalent hydrocarbon group having two carbon atoms. Each D ¹ can be independently linear or branched. For example, if D ¹ has two carbon atoms, then D ¹ has the formula C ₂ H ₄ and can be linear (CH ₂ CH ₂ ) or branched chain (CH CH ₃ ). .. In certain embodiments, D ¹ is linear. When the silicone polyether copolymer is prepared in bulk, in certain embodiments, at least 90 mole% of D ¹ is linear. In certain embodiments, each D ¹ is C ₂ H ₄ .

Each Y is a polyether moiety. Each Y is independently selected and can be any polyether moiety that contains at least one, and optionally at least two, ether moieties. Each Y can be the same as any or each other's Y. Alternatively, the silicone-polyether copolymer may contain at least two Ys that are different from each other. Y can be linear or branched. Y can have a divalent, trivalent, tetravalent, or valence greater than 4. Valence refers to the number of YX bonds present in the silicone polyether copolymer under the context of the polyether moiety Y. In certain embodiments, the polyether moiety Y is divalent such that the silicone polyether copolymer has the formula XYX. In other embodiments, the valence of the polyether moiety may exceed 2, in which case the polyether moiety Y is typically branched.

Each Y typically comprises a polyether having the general formula −O− (C _n H _2n O) _w −, in which the subscript n is independent of 2-4 in each portion represented by the subscript w. The subscript w is 1 to 1000. In certain embodiments, Y comprises a plurality of polyethers of this general formula, present in a linear or branched manner with other polyethers, and a polyether moiety Y containing a plurality of oxyalkylene-based polyethers. Can form. In such embodiments, Y'is oxyethylene units (C ₂ H ₄ O), oxypropylene units (C ₃ H ₆ O), oxybutylene or oxytetramethylene units (C ₄ H ₈ O), or mixtures thereof. Can include, which can be in block form at Y'or can be randomized. The oxyalkylene unit in Y can independently be linear or branched. For example, the oxyethylene unit, if present, can be of formula-CH ₂ CH ₂ O-, or of formula -CHCH ₃ O-. Similarly, the oxypropylene unit can be of the formula -CH ₂ CH ₂ CH ₂ O-, -CH ₂ CHCH ₃ O-, or -CHCH ₃ CH ₂ O-.

For example, Y may include a polyether having the general formula −O− (C ₂ H ₄ O) _x (C ₃ H ₆ O) _y (C ₄ H ₈ O) _z −, and the subscript x is 0. ~ 999, the subscript y is 1-1000, the subscript z is 0-999, and the units represented by the subscripts x, y, and z are randomized in Y. Or it can be in block form. In certain embodiments, x and z are each 0, polyethers Y have the general formula _{-O- (C 3 H 6 O)} y - has, y is as defined above.

In some embodiments, Y has the formula ^{_{-D 2 -O- (C n H 2n}} O) w -D 2 - having. In such an embodiment, each D ² has 1 to 6 carbon atoms, 1 to 5 carbon atoms in place, 1 to 4 carbon atoms in place, and 1 to 2 carbon atoms in place. It is an independently selected divalent hydrocarbon group having. Each D ² can be independently linear or branched. For example, if D ² has two carbon atoms, then D ² has the formula C ₂ H ₄ and can be linear (CH ₂ CH ₂ ) or branched chain (CH CH ₃ ). .. In certain embodiments, D ² is linear. Any D ² can be the same as or different from any particular D ¹ . In certain embodiments, each D ² is CH ₂ . Each subscript n is independently selected from 2-4 in each portion indicated by the subscript w, and the subscript w is defined above.

For example, in such embodiments, Y has the formula ^{_{-D 2 -O- (C 2 H 4}} O) x (C 3 H 6 O) y (C 4 H 8 O) z -D 2 - can have, The subscript x is 0-999, the subscript y is 1-1000, the subscript z is 0-999, and the units represented by the subscripts x, y, and z are , Y can be randomized or block form. In certain embodiments, x and z are each 0, Y has the formula ^{_{-D 2 -O- (C 3 H 6}} O) y -D 2 - has, ^{D 2} and y is defined above Will be done. In certain embodiments, each D ² is further C ₃ H ₆ . When x and z are each 0, and each ^{D 2} _is a C 3 _{H 6,} Y has the formula _{-C 3 H 6 -O- (C 3} H 6 O) y -C 3 H 6 Has − and y is defined above.

In certain embodiments, Y has the following general formula:
−CH ₂ −CH (R ³ ) − [D ² ] _{m −} O − [C ₂ H ₄ O] _x [C ₃ H ₆ O] _y [C ₄ H ₈ O] _z − [D ² ] _m −CH (R ³ ) -CH _2- ,
In the formula, each R ³ is an independent hydrocarbyl group, alkoxy group, silyl group, or H having 1 to 6 carbon atoms, and each D ² is an independent hydrocarbyl group having 1 to 6 carbon atoms. The divalent group selected, the subscript m is 0 or 1, the subscript x is 0-999, the subscript y is 1-1000, and the subscript z. Is 0-999, and the units represented by the subscripts x, y, and z can be in randomized or block form in the polyether moiety Y.

Each R ³ is independently selected may be any C ₁ -C _6, hydrocarbyl groups are described herein. Thus, any R ³ can be the same as or different from any particular R ¹ and / or R ² . For example, R ³ can be methyl, propyl and the like. In certain embodiments, each R ³ is methyl. Alternatively, or in addition, R ³ can be an H, alkoxy group, or silyl group.

Each subscript m is independently 0 or 1, and Y may include D ² of a divalent hydrocarbon group of 0, 1, or 2. Typically, each subscript m is 1. However, in certain embodiments, the at least one subscript m is 0.

In some embodiments, Y is branched, as described above. In such an embodiment, Y may have the general formula [D ² ] _m' [P], in which D ² is defined above and the subscript m'is ≧ 3 (eg, for example). 3, 4, 5, 6, 7, 8, 9, 10, etc.), where P is a polyether containing at least one of the above-mentioned polyethers. For example, in some such embodiments, P is a polyol (e.g., butanediol, glycerol, sorbitol, etc.), and polyoxyalkylene (e.g., polyoxypropylene) a polyether formed from, for D ² parts End protected with a number of m'. In such cases, the number of alcohol functional groups constituting the polyol will correspond to the maximum number of m'. However, if all polyoxyalkylene chains extending from the polyol are not end protected, m'will be less than the number of alcohol functional groups that make up the polyol.

Each Y usually has a number average molecular weight (M _n ) of at least about 100. In certain embodiments, at least one Y has at least 200, at least 300 alternatives, at least 400 alternatives, at least 500 alternatives, at least 600 alternatives, and at least 700 alternatives. In these or other embodiments, each Y is at least 200, at least 300 alternative, at least 400 alternative, at least 500 alternative, at least 600 alternative, at least 700 alternative, at least 1 alternative. 000, at least 2,000 alternatives, at least 4,000 alternatives, at least 8,000 alternatives, at least 12,000 alternatives, at least 16,000 alternatives, at least 25,000 alternatives Alternatively, it has at least 50,000 Mn. The number average molecular weight can be easily determined using gel permeation chromatography (GPC) techniques based on polystyrene standards.

Each Z is an independently selected siloxane moiety having the formula [R ¹ _h SiO _{(4-h) / 2} ] _d . In each siloxane portion Z, R ¹ is as defined above. Each subscript d is 1 to 1000, such as 1 to 500, 1 to 300 alternatives, 1 to 100 alternatives, 1 to 50 alternatives, 1 to 10 alternatives, and so on. Each subscript h is independently selected from 0 to 2 in each portion indicated by the subscript d, such as 0, 1, or 2. Each siloxane portion Z may independently contain a linear siloxane, a branched siloxane, or both. Similarly, any particular siloxane moiety Z may itself contain linear or branched compartments, or may include both linear and branched compartments. Thus, Z can be a linear siloxane moiety, a branched siloxane moiety, or a siloxane moiety that contains at least one linear and further at least one branched compartment. In certain embodiments, Z is branched (ie, includes at least one branched compartment).

In certain embodiments, each polyether moiety Y is linear and the silicone polyether copolymer may have one of the following structures:
Each X, Y, Z, and subscript c is defined above. Alternatively, each polyether portion Y can be branched. For example, a silicone-polyether copolymer may have one of the following structures:
Each X, Y, Z, and subscript c is defined above. As shown in these structures, each siloxane moiety Z can be linear or branched. In certain embodiments, both the polyether moiety Y and the siloxane moiety Z can be branched and the silicone polyether copolymer can have one of the following structures:
Each X, Y, Z, and subscript c is defined above.

In some embodiments, each polyether moiety Y and each siloxane moiety Z is linear and the silicone polyether copolymer has the following structure:

In the equation, each Y, R ¹ , subscript c, and subscript d are as defined above. For example, in some such embodiments, where each X has formula (I), the silicone-polyether copolymer has the following structure:
In the formula, each Y, R ¹ , R ² , D ¹ , subscript a, subscript b, subscript c, subscript d, subscript e, and subscript f are defined above. As it was done.

In a particular embodiment, X has formula (I) and e is 1. In these embodiments, the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript b, subscript c, subscript d, and subscript f are as defined above. .. In some such embodiments, f is 0 and the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript b, subscript c, and subscript d are as defined above. In some of these embodiments, b is 0 and the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript c, and subscript d are as defined above. In other embodiments, b is 1, and the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript c, and subscript d are as defined above. In other embodiments, f is 1, b is 1, and the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript b, subscript c, and subscript d are as defined above.

In some embodiments, X has formula (I) and e is 2. In these embodiments, the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript b, subscript c, subscript d, and subscript f are as defined above. .. In some such embodiments, f is 0 and the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript b, subscript c, and subscript d are as defined above. In some of these embodiments, b is 1, and the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript c, and subscript d are as defined above. In other embodiments, b is 0 and the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript c, and subscript d are as defined above. In other embodiments, f is 1, b is 1, and the silicone-polyether copolymer has the following structure:
In the equation, each Y, R ¹ , R ² , D ¹ , subscript a, subscript c, and subscript d are as defined above.

When each X has formula (II), the silicone polyether copolymer has the following structure:
In the equation, each Y, R ¹ , D ¹ , subscript a, subscript t, and subscript u are as defined above. In such an embodiment, X comprises an annular portion. In certain embodiments, (t + u) is 2-14, 2-9 alternatives, 2-6 alternatives, 2-5 alternatives, 2-4 alternatives.

The above exemplary structure is based on the fact that each X, each Y, and / or each Z in the silicone polyether copolymer is the same. However, as described above, each X, each Y, and each Z is independently selected. Therefore, one of ordinary skill in the art will readily understand the structures associated with silicone-polyether copolymers based on the selection of each X, each Y, and / or each Z.

Also disclosed are methods of preparing silicone-polyether copolymers. In this method, a polyether compound having two or more terminal unsaturated groups on average, a chain-extending organic silicone compound, and a terminal-protected organic silicone compound are reacted in the presence of a hydrosilylation catalyst to form a silicone polyether. Includes obtaining copolymers.

As will be appreciated by those skilled in the art in light of the description herein, the polyether compounds utilized in this method form a portion of the silicone-polyether copolymer corresponding to the polyether moiety Y and this method. The chain-extending organic silicone compound used in is part of a silicone polyether copolymer corresponding to the siloxane moiety Z, and the end-protected organic silicone compound used in this method is a silicone corresponding to the silicone moiety X. Form part of a polyether copolymer.

Typically, the polyether compound has the formula: Y ¹ [R ⁴ ] _i , where each R ⁴ is an independently selected unsaturated group having 2 to 14 carbon atoms. , The subscript i is> 1, and Y ¹ is a polyether moiety containing at least one polyether group.

Each R ⁴ is an independently selected unsaturated group with 2 to 14 carbon atoms. Typically, R ⁴ is either contains an alkenyl group or an alkynyl group, an alternatively alkenyl or alkynyl group. As a concrete example _{H 2 C = CH-, H 2} C = CHCH 2 -, H 2 C = CHCH 2 CH 2 -, H 2 C = CH (CH 2) 3 -, H 2 C = CH ( _{CH 2) 4 -, H 2} C = C (CH 3) -, H 2 C = C (CH 3) CH 2 -, H 2 C = C (CH 3) CH 2 CH 2 -, H 2 C = C (CH ₃ ) CH ₂ CH (CH ₃ )-, H ₂ C = C (CH ₃ ) CH (CH ₃ ) CH _2- , H ₂ C = C (CH ₃ ) C (CH ₃ ) _2- , HC ≡ Includes C-, HC≡CCH _2- , HC≡CCH (CH ₃ )-, HC≡CC (CH ₃ ) _2- , and HC≡CC (CH ₃ ) ₂ CH _2- .

In a particular embodiment, each R ⁴ has the formula CH ₂ C (R ³ )-[D ² ] _m- , in which each R ³ has an independent hydrocarbon having 1 to 6 carbon atoms. A group, an alkoxy group, a silyl group, or H, each D ² being an independently selected divalent group having 1 to 6 carbon atoms, with the subscript m being 0 or 1. is there. In certain embodiments, R ³ is -CH ₃ . In these or other embodiments, D ² is −CH ₂₋ . In a particular embodiment, each R ⁴ is H ₂ C = C (CH ₃ ) CH _2- .

The subscript i is> 1, such as 2, 3, 4, 5, 6, and so on. In general, the polyether compound, the subscript i is to correspond to the valence of Y ^1, includes R ⁴ at each end of the Y ^1, which is at least 2, in accordance with its branches 3 It can be 4, 5, or more.

Each Y ¹ is a polyether moiety that contains at least one polyether group, such as any of the above-mentioned polyether groups. Typically, the polyether group of Y ¹ has the general formula −O− (C _n H _2n O) _w −, and the subscript n is 2-4 in each portion represented by the subscript w. The subscript w is 1 to 1000, which is selected independently of. In certain embodiments, the at least one polyether group of Y ¹ has the formula −O− [C ₂ H ₄ O] _x [C ₃ H ₆ O] _y [C ₄ H ₈ O] _z −. , In the formula, each subscript x is 0 to 999, each subscript y is independently 1 to 1000, and each subscript z is independently 0 to 999. The units indicated by the subscripts x, y, and z can be in randomized or block form on the polyether group.

In some embodiments, Y ¹ is branched and has the general formula [R ⁴ ] _i' [P], in which R ⁴ is defined above and the subscript i 'Is ≧ 3 (eg, 3, 4, 5, 6, 7, 8, 9, 10, etc.) and P is a branched polyether containing at least one of the above-mentioned polyethers. For example, in some such embodiments, P is a poly formed from a polyol (eg, butanediol, glycerol, sorbitol, etc.) and a few or more polyoxyalkylenes (eg, polyoxypropylene). an ether, is end capped with a number of R ⁴ parts of i '. In such cases, the number of alcohol functional groups constituting the polyol will correspond to the maximum number of i'. However, if all polyoxyalkylene chains extending from the polyol are not end protected, i'will be less than the number of alcohol functional groups that make up the polyol.

In certain embodiments, the polyether compound is linear and i = 2, the polyether compound has the formula R ^4- Y ^1- R ⁴ , where Y ¹ and each R ⁴ are , As defined above. For example, in some such embodiments, the polyether compound has the following formula:
CH ₂ C (R ³ )-[D ² ] _m- O- [C ₂ H ₄ O] _x [C ₃ H ₆ O] _y [C ₄ H ₈ O] _z- [D ² ] _m- C (R) ³ ) CH _2,

In the equation, each R ³ , D ² , subscript m, subscript x, subscript y, and subscript z are as defined above. In certain embodiments, each R ³ is methyl, each D ² is CH ₂ , and each subscript m is 1. In these or other embodiments, the subscripts x and z are 0, respectively, and the polyether portion of the polyether compound contains only oxypropylene units.

The chain-extending organic silicone compound is typically an organohydrogensiloxane having at least two terminal silicone-bonded H groups. However, chain-extended organic silicone compounds can be branched and have 3, 4, or more terminal silicone-bonded H groups. For example, a chain-extended organic silicone compound may have one of the following formulas:
In the formula, Z'is a siloxane moiety and each R ¹ is as defined above. Thus, chain-extended organic silicone compounds typically include linear hydride silicone functional organic silicone compounds, branched hydride silicone functional organic silicone compounds, or both.

In some embodiments, the chain extender of the organosilicone compound has the formula comprises ^{_{[R 1 h 'SiO (4}} -h') / 2] ' siloxane moiety Z' _d, subscript d 'is 1 1000, the subscript h'is independently selected from 0 to 2 in each portion indicated by the subscript d', and R ¹ is as defined above. In such embodiments, the chain-extending organic silicone compound typically comprises a hydride bound to the terminal silicone atom of the siloxane moiety Z', a terminal silyl group having a silicone-bonded H atom, or a combination thereof.

In certain embodiments, the siloxane moiety Z'is linear and the chain-extending organic silicone compound is an organohydrogensiloxane having the following formula:
In the formula, each R ¹ is as defined above, and the subscript d'is 1-999.

As introduced above, the end-protected organic silicone compounds utilized in this method form the silicone moieties X of formulas (I) and (II) above. Thus, the end-protected organic silicone compound can be any organic silicone compound suitable for forming silicone-polyether copolymers, as is understood in the art. Typically, the end-protected organic silicone compound is an organohydrogensiloxane compound containing at least one silicone-bonded hydrogen atom. Silicon-bonded hydrogen atoms of the organohydrogensiloxane compound is reacted with unsaturated group R ⁴ of the polyether compound via a hydrosilylation reaction in the presence of a hydrosilylation catalyst utilized in this way.

In certain embodiments, the end-protected organic silicone compound is an organohydrogensiloxane compound having one of formulas (III) and (IV):
In the formula, each R ¹ , R ² , D ¹ , subscript a, subscript b, subscript e, subscript f, subscript t, and subscript u are defined above. That's right.

As will be readily appreciated in the art, the organohydrogensiloxane of formula (III) results in a siloxane moiety of formula (I) in a silicone polyether copolymer, and the organohydrogensiloxane of formula (IV) is a silicone. It provides the siloxane moiety of formula (II) in the polyether copolymer.

The organohydrogensiloxane compounds of formulas (III) and (IV) can be made via any suitable technique. Organohydrogensiloxanes can be prepared according to the methods disclosed in US Provisional Patent Application Publication Nos. 62/524637, 62/524636, and 62/524639, the subjects of which are described herein by reference. Is incorporated into.

As is understood in the art, the polyether compound, the chain-extending organic silicone compound, and the end-protected organic silicone compound can be reacted in any order or combination to give a silicone polyether copolymer. .. In certain embodiments, the method reacts a polyether compound with a chain-extending organic silicone compound in the presence of a hydrosilylation catalyst to give a siloxane polyether compound (ie, a chain-extending silicone polyether compound). And reacting the siloxane polyether compound with the end-protected organic silicone compound in the presence of a hydrosilylation catalyst to obtain a silicone polyether copolymer. The siloxane polyether compound can be prepared by any suitable technique. For example, in certain embodiments, the siloxane polyether compound is a siloxane polyether compound obtained by reacting a polyether compound having two terminal unsaturated groups with a chain-extending organic silicone compound in the presence of a hydrosilylation catalyst. Prepared by obtaining.

Siloxane polyether compound utilized in such an embodiment, the formula [Z _j Y _o] form part of a silicone polyether copolymer having the _c, Z, Y, subscript c, subscript j, subscript The letter o is defined above. For example, when the polyether moiety Y and the siloxane moiety Z are linear, the siloxane polyether compound may have the following formula:
In the equation, each Y, R ¹ , subscript c, and subscript d are as defined above. Therefore, the siloxane-polyether compound utilized is a silicone-polyether copolymer based on, for example, the molecular weight, the specific structure of each Y (ie, the unit in), the degree of polymerization of the syroxy unit represented by the subscript d, and the like. Can be selected based on the desired structure of.

In certain embodiments, the siloxane polyether compound has the following formula:

In such embodiments, each Y ¹ and R ¹ is as defined above, typically with the subscript c being 1-100, alternative 1-50, alternative 1-25. , Alternatives 1-10, Alternatives 1-5, etc., 1-150. Typically, each subscript d is 1 to 500, 1 to 300 alternatives, 1 to 100 alternatives, 1 to 50 alternatives, alternatives, in each portion represented by the subscript c. 1 to 1000, such as 1 to 10.

Polyether compounds and chain-extended organic silicone compounds typically have 1.001: 1-2: 1, alternative 1.4: 1-1.7: 1, and alternative 1.05: 1. The reaction is carried out at a molar ratio of ~ 1.5: 1, an alternative 1.1: 1 to 1.2: 1, and an alternative 1.2: 1 to 1.5: 1. The siloxane polyether compound is typically formed by the molar ratio of the polyether compound and the chain-extending organic silicone compound to reach the desired value of the subscript c.

Silicone polyether compounds and end-protected organic silicone compounds typically have a molar ratio of 1.5: 1-1 to the unsaturated group of the silicone polyether and the hydride silicone group of the end-protected organic silicone compound. : 1.5, Alternative 1.4: 1-1: 1.4, Alternative 1.3: 1-1: 1.3, Alternative 1.2: 1-1: 1.2, Alternatively, the reaction is 1.1: 1 to 1: 1.1, and the alternative is 1.1: 1 to 1: 1. When the silicone polyether is bifunctional, the silicone polyether copolymer is typically formed with a molar ratio of 1: 2 between the silicone polyether compound and the end-protected organic silicone compound, but on the other hand. On the other hand, one of the molar excesses may be used.

In certain embodiments, the method reacts a polyether compound with a terminal-protected organic silicone compound in the presence of a hydrosilylation catalyst to give a terminal-protected silicone polyether compound, in the presence of a hydrosilylation catalyst. It involves reacting an end-protected silicone polyether compound with a chain-extending organic silicone compound to obtain a silicone polyether copolymer. In these or other embodiments, the method reacts at least a portion of the polyether compound with a portion of the end-protected silicone polyether compound to give the end-protected silicone polyether compound, each described above. As such, at least a portion of the polyether compound and a portion of the chain-extending organic silicone compound are further reacted to obtain a siloxane polyether compound.

The hydrosilylation reaction catalyst is not limited, but can be any known hydrosilylation reaction catalyst for catalyzing the hydrosilylation reaction. A combination of different hydrosilylation reaction catalysts can be utilized.

In certain embodiments, the hydrosilylation reaction catalyst comprises a Group VIII to Group XI transition metal. Group VIII to Group XI transition metals refer to the modern IUPAC nomenclature. The transition metals of the VIII genus are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs), and the transition metals of the IX genus are cobalt (Co), rhodium (Rh), and The transition metals of the genus X are nickel (Ni), palladium (Pd), and platinum (Pt), and the transition metals of the genus XI are copper (Cu) and silver (Ag). , And gold (Au). Their combinations, their complexes (eg organometallic complexes), and other forms of such metals can be utilized as hydrosilylation reaction catalysts.

Additional examples of suitable catalysts for hydrosilylation reaction catalysts include renium (Re), molybdenum (Mo), Group IV transition metals (ie, titanium (Ti), zirconium (Zr), and / or hafnium (Hf)). ), Lantanide, actinide, and metal complexes of Group I and Group II (including, for example, calcium (Ca), potassium (K), strontium (Sr), etc.). Their combinations, their complexes (eg organometallic complexes), and other forms of such metals can be utilized as hydrosilylation reaction catalysts.

The hydrosilylation reaction catalyst can be in any suitable form. For example, the hydrosilylation reaction catalyst can be solid, including platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, as well as nickel-based catalysts. Specific examples of them include nickel, palladium, platinum, rhodium, cobalt, and similar elements, as well as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and. Includes similar catalysts containing combinations of multiple metals. Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts.

The hydrosilylation reaction catalyst can be in or on a solid support. Examples of carriers include activated carbon, silica, silica alumina, alumina, zeolites, and other inorganic powders / particles (eg, sodium sulfate, etc.). The hydrosilylation reaction catalyst can also be placed in a vehicle, eg, a solvent that solubilizes the hydrosilylation reaction catalyst, an alternative vehicle that simply carries the hydrosilylation reaction catalyst but does not solubilize. Such vehicles are known in the art.

In certain embodiments, the hydrosilylation reaction catalyst comprises platinum. In these embodiments, the hydrosilylation reaction catalyst is, for example, platinum black, a compound such as chloroplatinic acid, chloroplatinic acid hexahydrate, a reaction product of chloroplatinic acid with a monovalent alcohol, platinum bis (ethyl). It is exemplified by acetoacetate), platinum bis (acetylacetonate), chloroplatinate, and complexes of such compounds with olefins or organopolysiloxanes, and platinum compounds microencapsulated in matrix or core-shell compounds. Microencapsulated hydrosilylation catalysts and methods for their preparation are also known in the art and are also known in the art, as illustrated in US Pat. Nos. 4,766,176 and 5,017,654. Is incorporated herein by reference in its entirety.

Complexes of platinum and organopolysiloxane suitable for use as a hydrosilylation reaction catalyst include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum. These complexes can be microencapsulated in the resin matrix. Alternatively, the hydrosilylation reaction catalyst may comprise a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum. The hydrosilylation reaction catalyst can be prepared by a method comprising reacting chloroplatinic acid with an aliphatic unsaturated organic silicone compound such as divinyltetramethyldisiloxane or an alkene-platinum-silyl complex. The alkene-platinum-silyl complex can be prepared, for example, by mixing 0.015 mol (COD) PtCl ₂ with 0.045 mol COD and 0.0612 mol HMeSiCl ₂ , where COD contains cyclooctadiene. Represent.

Additional examples of hydrosilylation catalysts suitable for the ingredients include, for example, US Pat. Nos. 3,159,601, 3,220,972, 3,296,291, 3,419,593, 3,516,946, 3,814,730, 3,989,668, 4,784,879, 5,036,117, and 5,175,325. The disclosure is incorporated herein by reference in its entirety.

The hydrosilylation reaction catalyst can further or optionally be a photoactivated hydrosilylation catalyst, which may initiate curing by irradiation and / or heat. The photoactivated hydrosilylation catalyst can be any hydrosilylation catalyst that can catalyze the hydrosilylation reaction, especially when exposed to radiation having a wavelength of 150-800 nanometers (nm).

Sealants containing silicone-polyether copolymers are also provided. More specifically, the sealant comprises (I) a copolymer containing a silicone polyether copolymer, and (II) a condensation reaction catalyst.

(II) The condensation reaction catalyst is not limited, but in some embodiments, it is exemplified by a tin catalyst, a titanium catalyst, a zirconate catalyst, and a zirconium catalyst. Common examples of suitable tin catalysts include organotin compounds having a tin valence of either +4 or +2 (eg, tin (IV) compounds and / or tin (II) compounds). Specific examples of tin (IV) compounds include dibutyltin dilaurate, dimethyltin dilaurate, di- (n-butyl) tin bisketonate, dibutyltin diacetate, dibutyltin maleate, dibutyltin diacetylacetonate, dibutyltin dimethoxydo, and carbomethoxyphenyl. Tin trisuberate, dibutyl tin dioctanoate, dibutyl tin diformate, isobutyl tin tricholate, dimethyl tin dibutyrate, dimethyl tin dineodeconoate, dibutyl tin dineodeconoate, triethyltin tartrate, dibutyl tin dibenzoate, butyl tin tri Ditin salts of carboxylic acids such as 2-ethylhexanoate, dioctyltindiacetate, tinoctylic acid, tinoleic acid, tinbutyrate, tinnaphthenic acid, dimethyltindichloride, combinations thereof, and / or partial hydrolysis products thereof. Is included. Additional examples of tin (IV) compounds are known in the art and are Matatin® 740 and Fascat® from the European Swiss Acima Specialty Chemicals, a business unit of The Dow Chemical Company. 4202, as well as LA, Formrez® UL-28 from Galata Chemicals of Hannville, etc. are commercially available. Specific examples of the tin (II) compound include tin (II) salts of organic carboxylic acids such as tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, and tin (II) dilaurate. Stannous octanoate, stannous oleate, stannous acetate, stannous lauronate, stannous stearate, stannous naphthenate, stannous hexanoate, stannous succinate, ditin caprylic acid Includes first tin salts of carboxylic acids such as monotin, and combinations thereof. Examples of suitable titanium catalysts include tetra-n-butyl titanate tetraisopropyl titanate, tetra-2-ethylhexyl titanate, tetraphenyl titanate, triethanolamine titanate, titanium esters such as organic siloxytitanium compounds, and titanium ethylacetate acetate. Includes diisopropoxydi (ethoxyacetoacetyl) titanium and dicarbonyl titanium compounds such as bis (acetoacetonyl) -diisopropoxytitanium (IV). Many of these titanium catalysts are commercially available, such as TX, Tizor ™ DC from Houston's Doft Ketal Specialty Catalysts LLC, Tizor ™ TnBT, and Tizor ™ 9000. In certain embodiments, the (II) condensation reaction catalyst is a titanium catalyst such as one of those exemplified above, eg, the sealant is a room temperature vulcanized sealant composition, or as a room temperature vulcanized sealant composition. Can be blended. The amount of the (II) condensation reaction catalyst present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer present in the sealant, the type and / or amount of any additional material, etc.). It depends and can be easily determined by one of ordinary skill in the art. Typically, the sealant is a condensation reaction catalyst (II) in an amount of 0.2-6, optionally 0.5-3 parts by weight, based on the total weight of the (I) copolymer present in the sealant. Including.

In some embodiments, the sealant further comprises one or more additives. Examples of suitable additives that may be present in the sealant include fillers, treatment agents (eg, filler treatment agents), cross-linking agents, adhesion promoters, surface modifiers, desiccants, bulking agents, rheological agents, etc. Flame retardant, plasticizer, end blocker, bonding agent, antioxidant additive, water release agent, pigment, rheology adjuster, carrier, tackifier, corrosion inhibitor, catalyst inhibitor, viscosity adjuster, UV absorber, Includes antioxidants, light stabilizers, etc., and combinations thereof.

In certain embodiments, the sealant comprises a filler. Fillers can be, or include, reinforcing fillers, bulk fillers, conductive fillers (eg, conductive, thermally conductive, or both), or combinations thereof. Examples of suitable reinforcing fillers include precipitated calcium carbonate and reinforcing silica fillers such as fume silica, silica airgel, silica xerogel, and precipitated silica. Certain suitable precipitated calcium carbonates include Winnofil® SPM from Solvay, and Ultrapflex® and Ultrapflex® 100 from Specialty Minerals, Inc. Examples of fumed silica are known in the art and are commercially available, such as those sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, USA. Examples of suitable bulking fillers include crushed quartz, aluminum oxide, magnesium oxide, crushed calcium carbonate such as calcium carbonate, precipitated calcium carbonate, zinc oxide, talc, diatomaceous earth, iron oxide, clay, mica, cauldron, titanium dioxide, etc. Includes zirconia, sand, carbon black, graphite, or a combination thereof. Examples of bulk fillers are known in the art and are described in WV, Berkeley Springs, U.S.A. S. It is commercially available, including ground quartz sold by Silica under the name MIN-U-SIL. Other examples of commercially available bulk fillers include CS-11 from Imerys, G3T from Huber, Specialty Minerals, Inc. Includes Pfinyl 402 from, and calcium carbonate sold under the name Omyacarb 2T from Omya. The amount of filler present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer present in the sealant, the type and / or amount of any additional material, etc.). It can be easily determined by a person skilled in the art. The exact amount of filler used in a particular implementation of the sealant also depends on whether more than one type of filler is used. Typically, if present, the sealant comprises an amount of 0.1-95, alternative 1-60, and alternative 1-20% by weight, based on the weight of the sealant.

In certain embodiments, the sealant comprises a treatment agent. Treatment of sealant additives, such as, but not limited to, fillers and other additives that may be present in the sealant (eg, physical desiccants, flame retardants, pigments, and / or water release agents). , Surface treatment) can be any treatment agent suitable for use. More specifically, solid and / or particulate additives can be treated with a treatment agent before being added to the sealant. Alternatively, or even more, solid and / or particulate additives can be treated in situ with a treatment agent. General examples of suitable treatment agents include alkoxysilanes, alkoxyfunctional oligosiloxanes, cyclic polyorganosiloxanes, hydroxyl functional oligosiloxanes (eg, dimethylsiloxane or methylphenylsiloxane), fatty acids (eg, calcium stearate, etc.). Stearic acid) and the like, and combinations thereof. Specific examples of the treatment agent include alkyl thiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents and the like, and combinations thereof.

In some embodiments, the treatment agent is a treatment agent for an organic silicone filler or comprises a treatment agent for an organic silicone filler. Examples of treatment agents for such organic silicone fillers are organic chlorosilanes, organic siloxanes, organic disilazanes (eg, hexaalkyldisilazanes), and organic alkoxysilanes (eg, CH ₃ Si (OCH ₃ ) ₃ , C ₆ ). H ₁₃ Si (OCH ₃ ) ₃ , C ₈ H ₁₇ Si (OC ₂ H ₅ ) ₃ , C ₁₀ H ₂₁ Si (OCH ₃ ) ₃ , C ₁₂ H ₂₅ Si (OCH ₃ ) ₃ , C ₁₄ H ₂₉ Si (OCH ₃ ) Contains compositions suitable for the treatment of silica fillers such as OC ₂ H ₅ ) ₃ , C ₆ H ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ and the like. In these or other embodiments, the treatment agent has the formula _^(X): R 10 A Si or an alkoxysilane having a ^(OR _{11) 4-A,} or contains it. In formula (X), the subscript A is an integer of 1-3 such as 1, 2, or 3, and each R ¹⁰ has 1 to 50 carbon atoms, alternatives to 8 to 30. It is an independently selected monovalent organic group, such as a carbon atom, an alternative monovalent hydrocarbon group having 8-18 carbon atoms, and an alternative 1-5 carbon atoms. R ¹⁰ can be saturated or unsaturated, and branched or unbranched. Alternatively, R ¹⁰ can be saturated and unbranched. R ¹⁰ is exemplified by alkyl groups such as methyl, ethyl, hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; alkenyl groups such as vinyl; and aromatic groups such as benzyl and phenylethyl. Each R ¹¹ is a saturated hydrocarbon group having 1 to 4 carbon atoms independently selected, and 1 to 2 carbon atoms instead. Specific examples of the treatment agent for the organic silicone filler include hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, and the like. Octadecyltriethoxysilane, and combinations thereof, are also included.

In some embodiments, the treatment agent is an alkoxy-functional oligosiloxane or comprises an alkoxy-functional oligosiloxane. Examples of suitable alkoxy-functional oligosiloxane, include those having the general formula _{^{(XI) :( R 12 O)}} B Si (OSiR 13 2 R 14) (4-B). In formula (XI), the subscript B is 1, 2, or 3. In certain embodiments, the subscript B is 3. Each R ¹² is an independently selected alkyl group. Each R ¹³ is an independently selected unsaturated monovalent hydrocarbon group having 1 to 10 carbon atoms. Each R ¹⁴ is an independently selected unsaturated monovalent hydrocarbon group having at least 10 carbon atoms.

In certain embodiments, the treatment agent is a hydrogen-bondable polyorganosiloxane or comprises a hydrogen-bondable polyorganosiloxane. Such treatment agents utilize multiple hydrogen bonds that are clustered and / or dispersed as a means of connecting compatibilized moieties to the surface of the sealant component to be treated (eg, filler). Suitable polyorganosiloxanes capable of hydrogen bonding have at least one silicone bonding group capable of hydrogen bonding per molecule on average, typically an organic group having multiple hydroxyl functional groups, at least one. It is selected from organic groups having an amino functional group and combinations thereof. In other words, hydrogen bondable polyorganosiloxanes typically utilize hydrogen bonds as the primary form of attachment to the filler. Therefore, in some embodiments, the polyorganosiloxane is unable to form a covalent bond with the filler. Polyorganosiloxanes may be free of condensable silyl groups (eg, silicone-bonded alkoxy groups, silazanes, and silanols). Examples of polyorganosiloxanes suitable for use in or as sealants include saccharide siloxane polymers, amino-functional polyorganosiloxanes, and combinations thereof. In certain embodiments, the sealant comprises a polyorganosiloxane containing a saccharide siloxane polymer.

The amount of treatment agent present in the sealant depends on various factors (eg, those present in the sealant (such as those treated with treatment agent) (I) the amount and / or type of copolymer, the type of any additional material and / Or quantity, etc.) and can be easily determined by one of ordinary skill in the art. Typically, the amount of treatment agent is the type of treatment agent selected, the type and / or amount of microparticles to be treated, treated before the microparticles are added to the sealant, or treated in-situ. It depends on the particle. Typically, if present, the sealant is an amount of 0.01-20, alternative 0.1-15, alternative 0.5-5% by weight, based on the weight of the sealant. Including.

In some embodiments, the sealant comprises a polymeric additive such as a cross-linking agent, a chain extender, a plasticizer, a terminal blocker, or a combination thereof. In general, suitable polymer additives include compounds having functional groups present in the (I) copolymer of the sealant, or functional groups present in another polymer additive reacting thereto. Certain polymer additives can be named based on their intended function (eg, cross-linking, chain extension, final blockade, etc.). However, it is understood that the particular polymer additives described herein may have multiple functions, as will be readily appreciated by those skilled in the art, and thus the functions may overlap between the types of polymer additives. I want to be. For example, suitable cross-linking agents include, on average, each molecule containing a compound having two or more substituents that react with the alkoxy group present in the (I) copolymer, and as a suitable chain extender. On average, each molecule contains a compound having an alkoxy group present in the (I) copolymer or a compound having two substituents that reacts with a group present in another polymer additive that has reacted with the (I) copolymer. included. Therefore, as will be appreciated by those skilled in the art, various compounds can be used as cross-linking agents and / or chain extenders. Similarly, various plasticizers exemplified by the particular plasticizers described below may also be available in or interchangeably with sealant crosslinkers and / or chain extenders.

In some embodiments, the sealant comprises a cross-linking agent. Some examples of suitable cross-linking agents include silane cross-linking agents having hydrolyzable groups, or partial or complete hydrolysis products thereof. Examples of such a silane cross-linking agent include those containing a silicone compound having a general formula (XII): R ¹⁵ _C Si (R ¹⁶ ) _(4-C) , in which each R ¹⁵ is an alkyl group or the like. Each R ¹⁶ is a hydrolyzable substituent, for example, an acyloxy group such as a halogen atom, an acetamido group, an acetoxy, an alkoxy group, an amide group, an amino group, which are independently selected monovalent hydrocarbon groups. , Aminooxy group, hydroxyl group, oxymo group, ketoximo group, or methylacetamide group, and the subscript C is 0 to 3, such as 0, 1, 2, or 3. Usually, the subscript C has an average value greater than 2. Alternatively, the subscript C has an average value in the range 3-4. Typically, each R ¹⁶ is selected independently of hydroxyl, alkoxy, acetoxy, amide, or oxime. Specific examples of suitable silane cross-linking agents include methyldiacetoxymethoxysilane, methylacetoxydimethoxysilane, vinyldiacetoxymethoxysilane, vinylacetoxydimethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydiethoxysilane, and combinations thereof. Is included.

In some embodiments, the cross-linking agent comprises acyloxysilane, alkoxysilane, ketoximosilane, oxymosilane, etc., or a combination thereof.

Examples of suitable acetoxysilane cross-linking agents include tetraacetoxysilanes, organic triacetoxysilanes, diorganodiacetoxysilanes, and combinations thereof. Acetoxysilane is an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl; an alkenyl group such as vinyl, allyl, or hexenyl; an aryl group such as phenyl, trill, or xsilyl; benzyl or 2-phenyl. It may contain an aralkyl group such as ethyl; and a fluorinated alkyl group such as 3,3,3-trifluoropropyl. Examples of acetoxysilanes include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, phenyltriacetoxysilane, octylriacetoxysilane, and dimethyldiacetoxysilane. Includes silanes, phenylmethyldiacetoxysilanes, vinylmethyldiacetoxysilanes, diphenyldiacetoxysilanes, tetraacetoxysilanes, and combinations thereof. In some embodiments, the cross-linking agent comprises a mixture comprising an organic triacetoxysilane, such as methyltriacetoxysilane, and ethyltriacetoxysilane.

Examples of suitable amino-functional alkoxysilanes suitable for use in or as cross-linking agents are H ₂ N (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ Si (OCH). ₂ CH ₃ ) ₃ , H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₃ Si (OCH ₃ ) ) ₃ , CH ₃ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₅ Si (OCH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₅ Si (OCH ₂ CH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ NH ( CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ SCH ₃ (OCH) ₃ ) ₂ , H ₂ N (CH ₂ ) ₂ SCH ₃ (OCH ₂ CH ₃ ) ₂ , H ₂ N (CH ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , H ₂ N (CH ₂ ) ₃ SCH ₃ (OCH) ₂ CH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₃ SCH ₃ (OCH ₂ CH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₅ SCH ₃ (OCH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₅ SCH ₃ (OCH ₂ CH ₃ ) ₂ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , H ₂ N ( CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₂ NH (CH) ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SCH ₃ (OCH ₂ CH ₃ ) ₂ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SCH ₃ (OCH ₂ CH ₃ ) ₂ , and combinations thereof.

Examples of suitable oxymosilane cross-linking agents are alkyltrioxymosilanes such as methyltrioxymosilane, ethyltrioxymosilane, propyltrioxymosilane, and butyltrioxymosilane; methoxytrioxymosilane, ethoxytrio. Alkoxytrioxymosilanes such as ximosilane, propoxytrioxymosilane; or alkenyltrioxymosilanes such as propenyltrioxymosilane or butenyltrioxymosilane; alkenyloxymosilanes such as vinyloxymosilane; Alkenylalkyldioxysilanes such as vinylmethyldioxymosilane, vinylethyldioxymosilane, vinylmethyldioxymosilane, or vinylethyldioxymosilane; or combinations thereof are included.

Examples of suitable ketoximosilane cross-linking agents include methyltris (dimethylketoximo) silane, methyltris (methylethylketoximo) silane, methyltris (methylpropylketoximo) silane, methyltris (methylisobutylketoximo) silane, ethyltris (dimethylketoximo). Silane, ethyltris (methylethylketoximo) silane, ethyltris (methylpropylketoximo) silane, ethyltris (methylisobutylketoximo) silane, vinyltris (dimethylketoximo) silane, vinyltris (methylethylketoximo) silane, vinyltris (methylpropylketoximo) ) Silane, Vinyltris (Methylisobutylketoximo) Silane, Tetraquis (Dimethylketoximo) Silane, Tetrakiss (Methylethylketoximo) Silane, Tetrax (Methylpropylketoximo) Silane, Tetraquis (Methylisobutylketoximo) Silane, Methylbis (Dimethylketoki) Shimo) silane, methylbis (cyclohexylketoximo) silane, triethoxy (ethylmethylketooxime) silane, diethoxydi (ethylmethylketooxime) silane, ethoxytri (ethylmethylketooxime) silane, methylvinylbis (methylisobutylketoximo) silane, Or a combination thereof is included.

In certain embodiments, the cross-linking agent comprises a dialkoxysilane such as a dialkyldialkoxysilane; a trialkoxysilane such as an alkyltrialkoxysilane; a tetraalkoxysilane; a partial or complete hydrolysis product thereof; or a combination thereof. .. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and combinations thereof. included. Examples of suitable tetraalkoxysilanes include tetraethoxysilanes. In certain embodiments, the cross-linking agent comprises methyltrimethoxysilane or is alternative to methyltrimethoxysilane.

In certain embodiments, the cross-linking agent is a polymer. For example, the cross-linking agent is bis (triethoxysilyl) hexane, 1,4-bis [trimethoxysilyl (ethyl)] benzene, bis [3- (triethoxysilyl) propyl] tetrasulfide, bis (trimethoxysilyl) hexane. ), Disilanes such as bis (triethoxysilyl) ethane, bis (trimethoxysilyl) ethane, and combinations thereof. In these or other embodiments, the cross-linking agent is, for example, a single cross-linking agent or a combination containing two or more different cross-linking agents based on a hydrolyzable substituent and other organic groups attached to the silicone. Possible, in the case of polymeric crosslinkers, siloxane units, structures, molecular weights, sequences, etc. are used.

The amount of cross-linking agent present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer present in the sealant (such as other polymer additives), the type and / or of any additional material. It depends on the amount, the type of cross-linking agent used, etc.) and can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises an amount of 0.5-15, alternative 1-10, and alternative 3-10% by weight, based on the weight of the (I) copolymer.

In some embodiments, the sealant comprises a plasticizer. Examples of suitable plasticizers include carboxylic acid esters (eg, esters), phthalates (eg, phthalates (s)), carboxylates (eg, carboxylates (s)), adipates (eg, adipates (s)). )), Or organic plasticizers such as those containing a combination thereof. Specific examples of suitable organic plasticizers include bis (2-ethylhexyl) terephthalate, bis (2-ethylhexyl) -1,4-benzenedicarboxylate, 2-ethylhexylmethyl-1,4-benzenedicarboxylate, and 1, , 2 Cyclohexanedicarboxylic acid, dinonyl ester (branched and linear), bis (2-propylheptyl) phthalate, diisononyl adipate, and combinations thereof.

In certain embodiments, the plasticizer is an ester having at least one group of formula per molecule on average:
In the formula, R ¹⁷ is a branched or linear group such as a hydrogen atom or a monovalent organic group (for example, an alkyl group of 4 to 15 carbon atoms or 9 to 12 carbon atoms instead. Valuable hydrocarbon group). In these or other embodiments, the plasticizer has at least two groups of the above formula attached to each carbon atom in the cyclic hydrocarbon on average for each molecule. In such an example, the plasticizer may have the following general formula:
In this formula, D is a carbocyclic group having 3 or more carbon atoms, optionally 3 to 15 carbon atoms, and can be unsaturated, saturated, or aromatic. The subscript E is 1-12. Each R ¹⁸ is a branched or linear independent monovalent hydrocarbon group such as an alkyl group of 4 to 15 carbon atoms (eg, an alkyl group such as methyl, ethyl, butyl). Each R ¹⁹ is an independent hydrogen atom or a branched or linear, substituted or unsubstituted monovalent organic group. For example, in some embodiments, at least one R ¹⁹ is a moiety containing an ester functional group.

In certain embodiments, the sealant comprises a polymeric plasticizer. Examples of polymeric plasticizers are alkenyl polymers (eg, obtained by polymerizing vinyl or allyl monomers via various methods); polyalkylene glycol esters (eg, diethylene glycol dibenzoate, triethylene glycol, di). Benzoate pentaerythritol ester, etc.); Polyester plasticizers (eg, dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid, and divalents such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol). (Derived from the alcohols of); polyethers each containing a polyether polyol having a molecular weight of 500 or more (eg, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.); polystyrene (eg, polystyrene, poly-alpha-methyl). Styrene and the like); polybutene and polybutadiene (eg, polyisobutylene, butadieneacrylonitrile, etc.); and polychloroprene. In various embodiments, the low molecular weight plasticizer and the high molecular weight polymer plasticizer may be present in combination in the sealant.

Suitable plasticizers are known in the art and are commercially available. Such plasticizers may be present in the sealant alone or in combination. For example, the plasticizer may be a dialkyl phthalate such as dibutyl phthalate (Eastman ™ DBP plasticizer), diheptyl phthalate, diisononyl phthalate, di (2-ethylhexyl) phthalate, or diisodecyl phthalate (DIDP), bis. (2-propylheptyl) phthalate (BASF Palatinol® DPHP), di (2-ethylhexyl) phthalate (Eastman ™ DOP plasticizer), dimethyl phthalate (Eastman ™ DMP plasticizer); diethyl phthalate (Eastman ™ DMP Plasticizer); butylbenzylphthalate, and bis (2-ethylhexyl) terephthalate (Eastman ™ 425 Plasticizer); benzyl, C7-C9 linear and branched alkyl esters 1, 2, benzenedicarboxylic acid (Ferro SANTICIZER® 261A), 1,2,4-benzenetricarboxylic acid (BASF Plastic® TOTM-I), bis (2-ethylhexyl) -1,4-benzenedicarboxy Rate (Eastman ™ 168 plasticizer); 2-ethylhexylmethyl 1,4-benzenedicarboxylate; 1,2cyclohexanedicarboxylic acid, dinonyl ester, branched and linear (BASF Hexamol® DINCH ); Diisononyl adipate; Trimeritate such as trioctyl remeritate (Eastman ™ TOTM plasticizer); Triethylene glycol bis (2-ethylhexanoate) (Eastman ™ TEG-EH plasticizer); Triacetin ( Eastman ™ Triacetin); non-aromatic dibasic acid esters such as dioctyl adipate, bis (2-ethylhexyl) adipate (Eastman ™ DOA plasticizer and Eastman ™ DOA plasticizer, Kosher), di-2 -Ethylhexyl adipate (BASF Plastic® DOA), dioctyl sebacate, dibutyl sebacate, diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl resinolate; tricresyl phosphate and tributyl phosphate, etc. Phosphoric acid; chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydride terphenyl; process oil; epoxidized soybean oyster Epoxy plasticizers such as benzyl epoxy stearate; tris (2-ethylhexyl) ester; fatty acid ester; and combinations thereof. Can include phthalates such as. Examples of other suitable plasticizers and their commercial sources include BASF Palamol® 652 and Eastman 168 Xtreme ™ plasticizers.

The amount of plasticizer present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer present in the sealant (such as other polymer additives), the type and / or of any additional material. It depends on the amount, the type of cross-linking agent used, etc.) and can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises an amount of 5 to 150 parts by weight of the plasticizer, based on the total weight of all components in the sealant. In certain embodiments, the sealant comprises an amount of 0.1-10% by weight of plasticizer based on the total weight of the sealant.

In some embodiments, the sealant comprises a bulking agent. Examples of suitable bulking agents include non-functional polyorganosiloxane such as those containing bifunctional units of the formula ^R ₂₀ 2 _{SiO 2/2,} and the formula ^R ₂₁ 3 SiD'- terminal units of the formula Medium, each R ²⁰ and each R ²¹ is an alkyl such as methyl, ethyl, propyl, and butyl; an alkenyl such as vinyl, allyl, hexenyl; an aryl such as phenyl, trill, xsilyl, naphthyl; by an aralkyl group such as phenylethyl. It is an independent monovalent organic group such as the exemplified monovalent hydrocarbon group, where D'is an oxygen atom or a divalent group. Non-functional polyorganosiloxanes are known in the art and are commercially available. Suitable non-functional polyorganosiloxanes are exemplified by, but not limited to, polydimethylsiloxane. Such polydimethylsiloxanes, include DOWSIL (R) 200 Fluids, USA, Mich, is commercially available from Dow Silicones Corporation of ^Midland, 5x10 -5 to 0.1, alternatively ^5x10 -5 ~0. 05, alternatives may have viscosities in the range 0.0125-0.06, m ² / s. The amount of bulking agent present in the sealant depends on a variety of factors (eg, the amount and / or type of (I) copolymer present in the sealant (such as other polymer additives), the type and / or type of any additional material. It depends on the amount, the type of cross-linking agent used, etc.) and can be easily determined by those skilled in the art. Generally, if present, the sealant comprises an amount of 0.1 to 10% by weight of bulking agent based on the total weight of the sealant.

In some embodiments, the sealant comprises a terminal blocker. Suitable end-blocking agents include M units, i.e., siloxane units of the formula R ²² ₃ SiO _1/2 , where each R ²² represents an independent monovalent organic group, such as a monovalent hydrocarbon group. Typical examples of such end-blocking agents are polyorganosiloxanes (eg, poly) that are terminal-blocked at one end with a triorganosilyl group, eg, (CH ₃ ) ₃ SiO−, and at the other end with a hydroxyl group. Those containing polydiorganosiloxane (such as dimethylsiloxane) are included. Other examples of suitable end-blockers are polydiorganosiloxanes with both hydroxyl and triorganosilyl end groups, such as those having more than 50% of all end groups as hydroxyl groups, optionally more than 75%. Is included. The amount of triorganosilyl groups present in such terminal blockers can vary and is typically used to regulate the elastic modulus of the reaction product prepared by the condensation reaction of the sealant. Without wishing to be bound by theory, it is believed that high concentrations of triorganosilyl end groups can provide a low modulus of elasticity for certain cured products. In some embodiments, the sealant end-blocking agent comprises a single end-blocking compound. However, in other embodiments, the sealant end-blocking agent comprises two or more different end-blocking compounds that differ from each other due to properties including, for example, structure, viscosity, average molecular weight, polymer units, sequences, or combinations thereof. .. The amount of terminal blocker present in the sealant depends on a variety of factors (eg, the amount and / or type of (I) copolymer present in the sealant (such as other polymer additives), the type and / of any additional material. Alternatively, it depends on the amount, type of terminal blocker used, etc.) and can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises an amount of 0-50, alternative 0-30, alternative 0-15 wt% based on the total weight of the (I) copolymer.

In certain embodiments, the sealant comprises a surface modifier. Suitable surface modifiers include adhesion promoters, strippers and the like, as well as combinations thereof. Typically, surface modifiers are utilized to alter the surface appearance of the sealant's reaction products. For example, surface modifiers can be used to enhance the surface gloss of such reaction products. Specific examples of suitable surface modifiers include polydiorganosiloxanes with alkyl and aryl groups. For example, DOWNSIL® 550 Fluid is a trimethylsiloxy-terminated poly (dimethyl / methylphenyl) siloxane with a viscosity of 0.000125 m ² / s, which is commercially available from the Doe Silicones Corporation. These and other examples of suitable surface modifiers include natural oils (plant or animal sources) such as flaxseed oil, tung oil, soybean oil, castor oil, fish oil, cannabis oil, cottonseed oil, oyster oil, rapeseed oil. Includes those obtained from), and combinations thereof.

In some embodiments, the surface modifier is an adhesion promoter. Suitable adhesion accelerators may include hydrocarbon oxysilanes such as alkoxysilanes, combinations of alkoxysilanes with hydroxy-functional polyorganosiloxanes, amino-functional silanes, epoxy-functional silanes, mercapto-functional silanes, or combinations thereof. .. Adhesion promoters are known in the art and may include silanes having the formula R ²³ _FR ²⁴ _G Si (OR ²⁵ ) _{4- (F + G)} , each R ²³ having at least 3 carbon atoms. It is an independent monovalent organic group; R ²⁴ contains at least one SiC binding substituent having a group that promotes adhesion, such as an amino, epoxy, mercapto, or acrylate group; each R ²⁵ is an independent monovalent. Is an organic group of (eg, methyl, ethyl, propyl, butyl, etc.); the subscript F has a value in the range 0-2; the subscript G is either 1 or 2; (F + G). ) Does not exceed 3. In certain embodiments, the adhesion accelerator comprises a partial condensate of the above silane. In these or other embodiments, the adhesion enhancer comprises a combination of an alkoxysilane and a hydroxyfunctional polyorganosiloxane.

In some embodiments, the adhesion promoter comprises an unsaturated or epoxy functional compound. In such embodiments, the adhesion promoter has the formula _{^{(XIII): R 26 H Si}} (OR 27) (4-H) possible or unsaturated or epoxy-functional alkoxysilanes such as those having, or include it , The subscript H is 1, 2, or 3, and the subscript H is 1. Each R ²⁶ is an independent monovalent organic group, provided that at least one R ²⁶ is an unsaturated organic group or an epoxy functional organic group. Epoxy-functional organic group of R ²⁶ is 3-glycidoxypropyl, and are exemplified by (epoxycyclohexyl) ethyl. Unsaturated organic group R ²⁶ is 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and vinyl, allyl, hexenyl, are exemplified by monovalent hydrocarbon groups of unsaturated such as undecylenyl. Each R ²⁷ is an independent saturated hydrocarbon group with 1 to 4 carbon atoms, or 1 to 2 carbon atoms instead. R ²⁷ is exemplified by methyl, ethyl, propyl, and butyl.

Specific examples of suitable epoxy functional alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl) ethyldimethoxysilane, (epoxycyclohexyl) ethyldiethoxysilane, And their combinations are included. Examples of suitable unsaturated alkoxysilanes are vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyl. Includes oxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof.

In some embodiments, the adhesion enhancer is an epoxy-functional siloxane, such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane (eg, one of those described above), or a hydroxy-terminated. Includes a physical blend of polyorganosiloxane and epoxy functional alkoxysilane. The adhesion accelerator may include a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the adhesion accelerator is 3-glycidoxypropyltrimethoxysilane and a mixture of the reaction product of hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or 3-glycidoxypropyltrimethoxy. Illustrated by a mixture of silane and hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

In certain embodiments, the adhesion promoters are H ₂ N (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ , H ₂ N (CH ₂ ). ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₃ Si ( OCH ₂ CH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₅ Si (OCH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₅ Si (OCH ₂ CH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH) ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH) ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ SCH ₃ (OCH ₃ ) ₂ , H ₂ N (CH ₂ ) ₂ SCH ₃ (OCH ₂ CH ₃ ) ₂ , H ₂ N (CH ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , H ₂ N (CH ₂ ) ₃ SCH ₃ (OCH ₂ CH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₃ SCH ₃ (OCH ₂ CH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₅ SCH ₃ (OCH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₅ SCH ₃ (OCH ₂ CH ₃ ) ₂ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ SCH ₃ ( OCH ₂ CH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ , C H ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SCH ₃ (OCH ₂ CH ₃ ) ₂ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SCH ₃ (OCH ₃ ) ₂ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ , N- (3- (trimethoxysilyl) propyl) ethylenediamine, etc., and amino functionalities exemplified by combinations thereof. Includes amino-functional silanes such as sex alkoxysilanes. In these or other embodiments, the adhesion enhancer comprises a mercaptofunctional alkoxysilane such as 3-mercaptopropyltrimethoxysilane, or 3-mercaptopropyltriethoxysilane.

Additional examples of surface modifiers include epoxyalkylalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, amino-substituted alkoxysilanes such as 3-aminopropyltrimethoxysilane, and optionally methyltrimethoxysilane. Includes an adhesion promoter, which is the reaction product of the alkylalkoxysilane.

In some embodiments, the surface modifier comprises a water release agent or is an alternative water release agent. Suitable water release agents are exemplified by fluorofunctional silicones, or fluorinated compounds such as fluorofunctional organic compounds. In certain embodiments, the sealant comprises a plurality of surface modifiers such as one or more adhesion promoters, one or more release agents, one or more natural oils, or a combination thereof.

The amount of surface modifier present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer present in the sealant, the type and / or amount of any additional material, the sealant is exposed. It depends on the curing conditions intended to be) and can be easily determined by those skilled in the art. In general, if present, the sealant is in an amount of 0.01-50, alternative 0.01-10, alternative 0.01-5 parts by weight, based on the total weight of all components in the sealant. Contains a surface modifier.

In certain embodiments, the sealant comprises a desiccant such as a physical desiccant (eg, an adsorbent), a chemical desiccant. In general, desiccants bind water and low molecular weight alcohols from various sources. For example, desiccants can bind by-products of condensation reactions involving (I) copolymers such as water and alcohol. Physical desiccants usually capture and / or adsorb such water and / or by-products, and chemical desiccants usually bind water and / or other by-products by chemical means (eg, via covalent bonds). To do. Examples of desiccants suitable for use in sealants include adsorbents such as those containing inorganic fine particles. Such adsorbents typically have a particle size of 10 micrometers or less, optionally 5 micrometers or less, and an average pore size sufficient to adsorb alcohols of water and low molecular weight alcohols (eg, 10 Å (eg, 10 Å). It has an angstrom) or less, an alternative average pore size of 5 Å or less, and an alternative average pore size of 3 Å or less. Specific examples of such adsorbents include zeolites (eg, chavasite, mordenite, and anacite), and alkali metal aluminosilicone, silica gel, silica magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof. Includes molecular sieves. Examples of commercially available desiccants are 3 Å (Angstrom) molecular sieves, sold under the trademark SYLOSIV® from Grace Davidson and under the trade name PURMOL from Zeochem in Ky, Louisville, USA. Also included are dry molecular sieves such as the 4 Å molecular sieve sold under the trade name Ducil zeolite 4A by Ineos Siliconas in Warrington, UK. Other examples of suitable desiccants include MOLSIV ADSORBENT TYPE 13X, 3A, 4A, and 5A molecular sieves, all of which are commercially available from UOP, Illinois, USA; SILIPORITE NK 30AP and 65xP molecular sieves from Philadelphia's Atofina; and Maryland, USA, W. et al. R. A molecular sieve available under various names from Grace. Examples of chemical desiccants include silanes as described above for cross-linking agents. For example, alkoxysilanes suitable as desiccants include vinyltrimethoxysilane, vinyltriethoxysilane, and combinations thereof. As will be appreciated by those skilled in the art, chemical desiccants are added to the sealant or part of the sealant (eg, if the sealant is a multi-part composition) and the sealant or portion thereof is watered. Can be kept absent. Therefore, the desiccant can be added to a portion of the sealant (eg, the dry portion) before the sealant is formed, thereby stabilizing the partial shelf. Alternatively or additionally, the desiccant can be kept water-free in the sealant after formulation (eg, after the portions of the sealant have been combined / mixed). The amount of desiccant present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer present in the sealant, the type and / or amount of any additional material, the exposure of the sealant. It depends on the intended curing conditions, etc.) and can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises an amount of 0.1 to 5 parts by weight of desiccant based on the total weight of all components in the sealant.

In some embodiments, the sealant comprises a biocide. Common examples of suitable biocides include fungicides, herbicides, pesticides, antibacterial agents and the like, and combinations thereof. For example, in certain embodiments, the biocide comprises or is a fungicide. Specific examples of bactericides include N-substituted benzimidazolyl carbamate and benzimidazolyl carbamate, such as methyl 2-benzimidazolyl carbamate, ethyl 2-benzimidazolyl carbamate, isopropyl 2-benzimidazolyl carbamate, methyl N- {2-[ 1- (N, N-dimethylcarbamoyl) benzimidazolyl]} carbamate, methyl N- {2- [1- (N, N-dimethylcarbamoyl) -6-methylbenzimidazolyl]} carbamate, methyl N- {2- [ 1- (N, N-dimethylcarbamoyl) -5-methylbenzimidazolyl]} carbamate, methyl N- {2- [1- (N-methylcarbamoyl) benzimidazolyl]} carbamate, methyl N- {2- [1- (N-methylcarbamoyl) -6-methylbenzimidazolyl]} carbamate, methyl N- {2- [1- (N-methylcarbamoyl) -5-methylbenzimidazolyl]} carbamate, ethyl N- {2- [1- (N, N-dimethylcarbamoyl) benzimidazolyl]} carbamate, ethyl N- {2- [2- (N-methylcarbamoyl) benzimidazolyl]} carbamate, ethyl N- {2- [1- (N, N-dimethyl) Carbamoyl) -6-methylbenzimidazolyl]} carbamate, ethyl N- {2- [1- (N-methylcarbamoyl) -6-methylbenzimidazolyl]} carbamate, isopropyl N- {2- [1- (N, N, N, N) -Dimethylcarbamoyl) benzimidazolyl]} carbamate, isopropyl N- {2- [1- (N-methylcarbamoyl) benzimidazolyl]} carbamate, methyl N- {2- [1- (N-propylcarbamoyl) benzimidazolyl]} Carbamate, methyl N- {2- [1- (N-butylcarbamoyl) benzimidazolyl]} carbamate, methoxyethyl N- {2- [1- (N-propylcarbamoyl) benzimidazolyl]} carbamate, methoxyethyl N- { 2- [1- (N-butylcarbamoyl) benzimidazolyl]} carbamate, ethoxyethyl N- {2- [1- (N-propylcarbamoyl) benzimidazolyl]} carbamate, ethoxyethyl N- {2- [1-( N-butylcarbamoyl) benzimidazolyl]} carbamate, methyl N- {1- (N, N-dimethylcarbamoyloxy) benzimidazolyl]} carbamate , Methyl N- {2- [N-methylcarbamoyloxy) benzimidazolyl]} carbamate, methyl N- {2- [1- (N-butylcarbamoyloxy) benzoimidazolyl]} carbamate, ethoxyethyl N- {2- [1 -(N-propylcarbamoyl) benzimidazolyl]} carbamate, ethoxyethyl N- {2- [1- (N-butylcarbamoyloxy) benzoimidazolyl]} carbamate, methyl N- {2- [1- (N, N-dimethyl)] Carbamoyl) -6-chlorobenzimidazolyl]} carbamate, methyl N- {2- [1- (N, N-dimethylcarbamoyl) -6-nitrobenzimidazolyl]} carbamate; 10,10'-oxybisphenoxalcin ( Brand name: Vinyzene, OBPA); Diiodomethylparatril sulfone; Benthiophene-2-cyclohexylcarboxamide-S, S-dioxide; N- (fluordichloride methylthio) phthalimide (trade name: Fluor-Foper, Presidentol A3); Methylbenzimideazole-2-ylcarbamate (trade name: Carbendazim, Presidentol BCM); zinc-bis (2-pyridylthio-1-oxide); zinc pyrithione; 2- (4-thiazolyl) -benzimidazole; N-phenyliodo Propargyl carbamate; N-octyl-4-isothiazolin-3-one; 4,5-dichloride-2-n-octyl-4-isothiazolin-3-one; N-butyl-1,2-benzoisothiazolin-3-one; Included are triazolyl compounds such as tebuconazole; and combinations thereof. In certain embodiments, such fungicides are utilized in combination with one or more inorganic materials such as minerals (eg, zeolites), metals (eg, copper, silver, platinum, etc.), and combinations thereof.

In certain embodiments, the biocide comprises a herbicide or is an alternative herbicide. Specific examples of the herbicide include amide herbicides such as alydochlor N, N-diallyl-2-chloroacetamide; CDEA2-chloro-N, N-diethylacetamide; etonipromid (RS) -2- [5- (2,4). -Dichlorophenoxy) -2-nitrophenoxy] -N-ethylpropionamide; anilide herbicides such as cisanilidesis-2,5-dimethylpyrrolidin-1-carboxanilide; flufenacet 4'-fluoro-N-isopropyl-2 -[5- (Trifluoromethyl) -1,3,4-thiasiazol-2-yloxy] acetoanilide; naproanilide (RS) -α-2-naphthoxypropionanilide; benzoylprop N-benzoyl-N- (3,4) -Dichlorophenyl) -arylalanine herbicides such as DL-alanine; flamprop-MN-benzoyl-N- (3-chloro-4-fluorophenyl) -D-alanine; butachlor N-butoxymethyl-2-chloro-2' Chloroacetanilide herbicides such as 6'-diethylacetanilide; metazachlor 2-chloro-N- (pyrazole-1-ylmethyl) aceto-2', 6'-xylidide; prinachlor (RS) -2-chloro-N- (1) -Methylprop-2-inyl) acetanilide; chloranthram 3-chloro-2- (5-ethoxy-7-fluoro [1,2,4] triazolo [1,5-c] pyrimidin-2-ylsulfonamide) benzoic acid, etc. Sulfonanilide herbicide; metoslam 2', 6'-dichloro-5,7-dimethoxy-3'-methyl [1,2,4] triazolo [1,5-a] pyrimidin-2-sulfonanilide; viranaphos 4- Antibiotics herbicides such as [hydroxy (methyl) phosphinoyl] -L-homoalanyl-L-alanyl-L-alanine; benzoic acid herbicides such as chloramben 3-amino-2,5-dichlorobenzoic acid; 2,3 6-TBA 2,3,6-trichlorobenzoic acid; bispyribak 2,6-bis (4,6-dimethoxypyrimidine-2-yloxy) pyrimidinyloxybenzoic acid herbic acid such as benzoic acid; pyrithiobac 2-chloro-6- ( 4,6-Dimethoxypyrimidin-2-ylthio) Pyrimidinylthiobenzoic acid herbicides such as benzoic acid; phthalic acid herbicides such as chlortaltetrachloroterephthalic acid; aminopyralid 4-amino-3,6-dichloropyridine-2- Picolinic acid herbicides such as carboxylic acid; kin Kinoline carboxylic acid herbicides such as chlorac 3,7-dichloroquinolin-8-carboxylic acid; arsenic herbicides such as CMA calcium bis (methylarsonate hydride); MAMA ammonium hydrogenmethylarsonate; sodium phosphite; mesotrione Benzoylcyclohexanedione herbicides such as 2- (4-mesyl-2-nitrobenzoyl) cyclohexane-1,3-dione; benzos such as benfresate 2,3-dihydro-3,3-dimethylbenzofuran-5-ylethanesulfonate Furanylalkylsulfonate herbides; carbamothelmethyl 5-tert-butyl-1,2-oxazol-3-ylcarbamate and other carbamate herbs; phenaslammethyl 4- [2- (4-chloro-o-) Trilloxy) acetamide] phenylsulfonylcarbamate; carboxylate herbicides such as BCPC (RS) -sec-butyl 3-chlorocarbanilate; desmedifamethyl 3-phenylcarbamoyloxyphenylcarbamate; swepmethyl 3,4-dichlorocarbanyl Acid; butroxydim (RS)-(EZ) -5- (3-butylyl-2,4,6-trimethylphenyl) -2- (1-ethoxyiminopropyl) -3-hydroxycyclohex-2-ene-1- Cyclohexene oxime herbicide such as on; teplaroxydim (RS)-(EZ) -2- {1-[(2E) -3-chloroallyloxyimino] propyl} -3-hydroxy-5-perhydropyran-4-yl Cyclohexa-2-ene-1-one; cyclopropylisooxazole herbicides such as isoxachlortol 4-chloro-2-mesylphenyl5-cyclopropyl-1,2-oxazol-4-ylketone; flumedin 2-methyl Dicarboxyimide herbs such as -4- (α, α, α-trifluoro-m-tolyl) -1,2,4-oxadiadinane-3,5-dione; ethaneflularin N-ethyl-α, α, Dinitroaniline herbicides such as α-trifluoro-N- (2-methylallyl) -2,6-dinitro-p-toluidine; prodiamine 5-dipropylamino-α, α, α-trifluoro-4,6- Dinitro-o-toluidine; dinitrophenol herbicides such as dinoprop 4,6-dinitro-o-simene-3-ol; ethinophen α-ethoxy-4,6-dinitro-o-cresol; ethoxyphen O- [2-chloro -5- (2-) Diphenyl ether herbicides such as chloro-α, α, α-trifluoro-p-triloxy) benzoyl] -L-lactic acid; nitrophenyl ether herbicides such as acronifen 2-chloro-6-nitro-3-phenoxyaniline; nitrophen 2 , 4-Dichlorophenyl 4-nitrophenyl ether; dithiocarbamate herbicides such as Dazomet 3,5-dimethyl-1,3,5-thiadiadinan-2-thione; halogenated aliphatics such as dalapon 2,2-dichloropropionic acid Herbicide; chloroacetic acid; imidazolinone herbicide such as imazapill (RS) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid; disodium tetraborate ten water Inorganic herbicides such as Japanese; sodium azide; nitrile herbicides such as chloroxinyl 3,5-dichloro-4-hydroxybenzonitrile; ioxinyl 4-hydroxy-3,5-diiodobenzonitrile; anilophos S-4-chloro -Organic phosphorus herbicides such as N-isopropylcarbaniloylmethyl O, O-dimethylphosphologithioate; gluhosinate 4- [hydroxy (methyl) phosphinoyl] -DL-homoalanine; clomeprop (RS) -2- (2, Phenoxy herbicides such as 4-dichloro-m-tolyloxy) propionanilide; phenoxyacetic acid herbicides such as fenteracol 2- (2,4,5-trichlorophenoxy) ethanol; MCPA (4-chloro-2-methylphenoxy) acetic acid Agents; phenoxybutyric acid herbicides such as MCPB 4- (4-chloro-o-tolyloxy) butyric acid; phenoxypropion herbicides such as phenoxyprop (RS) -2- (2,4,5-trichlorophenoxy) propionic acid; Isooxapyrifops (RS) -2- [2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionyl] aryloxyphenoxypropion herbicides such as isooxazolidine; dinitramine N1, N1- Phenoxyamine herbicides such as diethyl-2,6-dinitro-4-trifluoromethyl-m-phenoxyaletic acid, pyrazoxifene 2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazole-5-yloxy ] Pyrazolyloxyacetphenone herbicide such as acetphenone; pyrafluphen 2-chloro-5- (4-chloro-5-difluoromethoxy-1-methylpyrazole-3-a) Pyrazolylphenyl herbicides such as -4-fluorophenoxyacetic acid; pyridazine herbicides such as pyridafol 6-chloro-3-phenylpyridazine-4-ol; chloridezone 5-amino-4-chloro-2-phenylpyridazine-3 ( Pyridadinone herbicides such as 2H) -one; oxapyrazone 5-bromo-1,6-dihydro-6-oxo-1-phenylpyridazine-4-yloxamic acid; fluoroxipyl 4-amino-3,5-dichloro-6- Pyridine herbicides such as fluoro-2-pyridyloxyacetic acid; thiazopylmethyl 2-difluoromethyl-5- (4,5-dihydro-1,3-thiazole-2-yl) -4-isobutyl-6-trifluoromethylnicotinate Pyrimidinediamine herbicides such as iprimidum 6-chloro-N4-isopropylpyrimidine-2,4-diamine; quaternary ammonium herbicides such as dietamquat 1,1'-bis (diethylcarbamoylmethyl) -4,4'-bipyridinium; Paracoat 1,1'-dimethyl-4,4'-bipyridinium; thiocarbamate herbicides such as cycloate S-ethylcyclohexyl (ethyl) thiocarbamate; thiocarbazyl S-benzyldi-sec-butylthiocarbamate; EXDO, O-diethyldithio Thiocarbonate herbicides such as bis (thioformate); thiourea herbicides such as methiulone 1,1-dimethyl-3-m-tolyl-2-thiourea; triazine-based (RS) -N- [2- (3,5) -Dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4 and other triazine herbicides-diamine; cyprazine 6-chloro-N2- Chlorotriazine herbicides such as cyclopropyl-N4-isopropyl-1,3,5-triazine-2,4-diamine; propazine 6-chloro-A2, N4-di-isopropyl-1,3,5-triazine-2, 4-Diamine; methoxytriazine herbicides such as Promethone N2, N4-di-isopropyl-6-methoxy-1,3,5-triazine-2,4-diamine; cyanatrin 2- (4-ethylamino-6-methylthio-) 1,3,5-Triazine-2-ylamino) -2-Methylthiotriazine herbicides such as propionitrile; hexadinone 3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2, 4 (1H, 3H) -ji Triazinone herbicides such as on; triazole herbicides such as apronaz N-ethyl-N-propyl-3-propylsulfonyl-1H-1,2,4-triazol-1-carboxamide; calfentrazone (RS) -2- Chloro-3-{2-chloro-5-[4- (difluoromethyl) -4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl] -4- Triazolone herbicides such as fluorophenyl} propionic acid; tria such as fluoroslam 2', 6', 8-trifluoro-5-methoxy [1,2,4] triazolo [1,5-c] pyrimidin-2-sulfonanilide Zoropyrimidine herbicide; flupropacylisopropyl 2-chloro-5- (1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-trifluoromethylpyrimidine-1-yl) benzoate, etc. Ulacyl herbicides; urea herbicides such as cyclone 3-cyclooctyl-1,1-dimethylurea; monisourone 1- (5-tert-butyl-1,2-oxazol-3-yl) -3-methylurea; chloroxlon 3 -Phenylurea herbicides such as 4- (4-chlorophenoxy) phenyl] -1,1-dimethylurea; sizzlon 1- (2-methylcyclohexyl) -3-phenylurea; frazasulfone 1- (4,6) -Pyrimidinylsulfonylurea herbicides such as −dimethoxypyrimidine-2-yl) -3- (3-trifluoromethyl-2-pyridylsulfonyl) urea; pyrazosulfone 5-[(4,6-dimethoxypyrimidine-2-ylcarbamoyl) sulfamoyl) ] -1-Methylpyrazole-4-carboxylic acid; thifensulfone 3- (4-methoxy-6-methyl-1,3,5-triazine-2-ylcarbamoyl sulfamoyl) thiophen-2-carboxylic acid, etc. Triazinylsulfonylurea herbicides; thiadiazolylurea herbicides such as tebutyurone 1- (5-tert-butyl-1,3,4-thiadiazol-2-yl) -1,3-dimethylurea; and / or chlorphenac (2) , 3,6-Trichlorophenyl) Unclassified herbicides such as acetic acid; Metazol 2- (3,4-dichlorophenyl) -4-methyl-1,2,4-oxadiazolidine-3,5-dione; Tritac ( RS) -1- (2,3,6-trichlorobenzyloxy) propan-2-ol; 2,4-D, chlorimlon, and phenoxaprop; The combination includes those combinations.

In some embodiments, the biocide comprises or is an alternative pesticide. Common examples of pesticides include insect repellents such as N, N-diethyl-meth-toluamide, and pyrethroids such as pyrethrin. Specific examples of pesticides include atrazine, diazinon and chlorpyrifos. In these or other embodiments, the biocide comprises an antibacterial agent or is an antibacterial agent. The type and nature of the antibacterial agent can be versatile and can be easily determined by those skilled in the art. Certain antibacterial agents are commercially available and include DOWNSIL® 5700 and DOWNSIL® 5772 obtained from Dow Silicones Corporation, Mitch, Midland, USA. In certain embodiments, the biocide optionally comprises a boron-containing material such as boric acid anhydride, borax, or disodium octaborate tetrahydrate. In various embodiments, the sealant comprises two or more biocides, each independently selected from the fungicides, herbicides, insecticides, antibacterial agents, and other biocide components exemplified herein. Including.

The amount of biocide present in the sealant can be determined by a variety of factors (eg, the type of biocide utilized, the amount and / or type of (I) copolymer, the intended use of the sealant, the exposure of the sealant. It depends on the intended curing conditions, etc.) and can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises a biocide or a combination of biocides in an amount of 0.01-10, alternative 0.1-5% by weight, based on the total weight of the sealant.

In certain embodiments, the sealant comprises a flame retardant. Examples of suitable flame retardants are organic / carbon flame retardants (eg carbon black), inorganic / mineral flame retardants (eg hydrated aluminum hydroxide, wollastonite and other silicates, platinum metal complexes and / Or platinum, etc.), and combinations thereof. Additional examples of suitable flame retardants include halogen-based flame retardants such as decabromodiphenyl oxide, octabromodiphenyl oxide, hexabromocyclododecane, decabromobiphenyl oxide, diphenoxybenzene, ethylenebistetrabromophthalimide, pentabromo. Ethylbenzene, pentabromobenzyl acrylate, imide tribromophenylmaleate, tetrabromobisphenyl A, bis- (tribromophenoxy) ethane, bis- (pentabromophenoxy) ethane, polydibophenylene phenylene, tribromophenylallyl ether dibromopropyl Ether, tetrabromophthalic anhydride, dibromoneopentyl glycol, dibromoethyldibromocyclohexane, pentabromodiphenyl oxide, tribromostyrene, pentabromochlorocyclohexane, tetrabromoxylene, hexabromocyclododecane, brominated polystyrene, tetradecabromodi Phenoxybenzene, trifluoropropene, and PVC; phosphorus flame retardants, such as (2,3-dibromopropyl) -phosphate, phosphorus, cyclic phosphate, triaryl phosphate, bis-melamineium pentato, pentaerythritol bicyclic phosphate. , Dimethylmethylphosphate, phosphine oxidediol, triphenylphosphate, tris- (2-chloroethyl) phosphate, phosphate esters such as tricrail, trixylenyl, isodecyldiphenyl, ethylhexyldiphenyl, trioctyl, tributyl, and trisbutoxyethyl phosphate, and Phosphates of various amines (eg ammonium phosphate); tetraalkyl lead compounds such as tetraethyl lead; pentacarbonyl iron; manganese methylcyclopentadienyltricarbonyl; melamine and derivatives thereof, such as melamine salts; guanidine; disyandiamide; sulfamine Includes ammonium acid; alumina trihydrate; magnesium hydroxide alumina trihydrate; and the like, as well as derivatives, variants and combinations thereof. The amount of flame retardant present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer, the intended use of the sealant, the curing conditions intended for the sealant to be exposed, the presence of vehicle / solvent. / None, etc.) and can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises an amount of 0.01-15, alternative 0.1-10% by weight, based on the total weight of the sealant.

In certain embodiments, the sealant comprises a bonding agent. Typically, the bonding agent is a non-reactive, elastomeric, organic polymer, i.e., an elastomeric organic polymer that does not react with the (I) copolymer. In addition, the bonding agent is typically compatible with the (I) copolymer, i.e., the bonding agent does not form a two-phase system when blended into the sealant with the (I) copolymer. In general, suitable bonding agents have low gas and moisture permeability and usually contain a number average molecular weight (Mn) of 30,000 to 75,000. However, the bonding agent may include a blend of various non-reactive and elastomeric organic polymers (eg, polymers with high molecular weight and those with low molecular weight). In such an example, the high molecular weight polymer (s) usually contain 100,000 to 600,000 Mn, the low molecular weight polymer (s) usually 900 to 10,000, and optionally 900 to 3, Contains 000 Mn. The lower limit of the Mn range is typically selected so that the bonding agent is compatible with the other components of the (I) copolymer and sealant, as will be appreciated by those skilled in the art. Does the bonding agent contain one organic polymer that is non-reactive and elastomeric, for example based on structure, viscosity, average molecular weight (Mn or Mw), polymer units, sequences, etc., or a combination thereof? , Or optionally, it may contain two or more different organic polymers that are non-reactive and elastomeric.

Examples of suitable bonding agents include polyisobutylene, which is known in the art and is commercially available. Specific examples of polyisobutylene include those sold under the trademark OPPANOL (registered trademark) by BASF Corporation in Germany, and NOF Corp. in Japan. It also contains hydrogenated polyisobutene such as various products sold under the trademark of PARLEAM (registered trademark). Additional examples of suitable polyisobutylene include Exxon Mobile Chemical Co., Ltd. of Baytown, USA. Is commercially available under the trademark VISTANEX®. These include VISTANEX® MML-80, MML-100, MML-120, and MML-140, which are paraffins composed of long linear polymers containing only chain-terminated olefin bonds. It is a system hydrocarbon polymer. VISTANEX® MM polyisobutylene has a viscosity average molecular weight of 70,000 to 90,000, and VISTANEX® LM polyisobutylene (eg, LM-MS) has a viscosity average of 8,700-10. It is a low molecular weight polyisobutylene having a molecular weight. Additional examples of polyisobutylene include VISTANEX LM-MH (viscosity average molecular weight of 10,000-11,700); Amoco Corp., Illinois, Chicago, USA. Soltex PB-24 (Mn 950), Indopol® H-100 (Mn 910), Indopol® H-1200 (Mn 2100); NAPVIS® from BP Chemicals, London, UK And HYVIS® (eg, NAPVIS® 200, D10, and DE3; and HYVIS® 200); NAPVIS® polyisobutylene typically has a Mn of 900 to 1300. As an addition or alternative to polyisobutylene, the bonding agent may include butyl rubber, styrene ethylene / butylene styrene (SEBS) block copolymer, styrene-ethylene / propylene-styrene (SEPS) block copolymer, polyolefin plastomer, or a combination thereof. Or they can be. SEBS and SEPS block copolymers are known in the art and are known in the art from Kraton Polymers U.S.A., Tex, Houston, USA. S. From LLC as Kraton® G Polymer and, USA, N. et al. Y, New York is commercially available as a Septon polymer from Kuraray America. Polyolefin plastomers are also known in the art and are commercially available as AFFINITY® GA 1900 and AFFINITY® GA 1900 and AFFINITY® from the Dow Chemical Company, Elastomers & Specialty Products Division of Midland, Mich, USA. There is.

The amount of bonding agent present in the sealant depends on a variety of factors (eg, the amount and / or type of (I) copolymer, the intended use of the sealant, the curing conditions intended for the sealant to be exposed, and the presence of vehicle / solvent. It depends on (/ none, etc.) and can be easily determined by those skilled in the art. Generally, if present, the sealant comprises an amount of 1 to 50, 5 to 40 alternatives, and 5 to 35 parts by weight of the sealant, based on the total weight of all components in the sealant.

In some embodiments, the sealant comprises an anti-aging additive. Examples of anti-aging additives include antioxidants, UV absorbers, UV and / or light stabilizers, heat stabilizers, and combinations thereof. The anti-aging additive may be one anti-aging additive or may include it, and may optionally include two or more different anti-aging additives. In addition, certain anti-aging additives can perform multiple functions (eg, as both UV absorbers and UV stabilizers, as both antioxidants and UV absorbers). Many suitable anti-aging additives are known in the art and are commercially available. For example, suitable antioxidants include phenolic antioxidants (eg, fully sterically hindered phenols and partially hindered phenols), and phenolic antioxidants and stabilizers (eg, "hindered amine light stabilizers". Also included are combinations with steric hindrance amines (HALS), such as tetramethylpiperidin derivatives. Suitable phenolic antioxidants include Vitamin E and IRGANOX® 1010 from BASF. IRGANOX® 1010 includes pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate). Examples of UV absorbers include branched and linear phenol, 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methyl- (TINUVIN® 571). .. Examples of UV stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; methyl 1,2,2,6,6-pentamethyl-4-piperidyl / sebacate; and combinations thereof. (TINUVIN® 272) are included. These and other TINUVIN® additives such as TINUVIN® 765 are commercially available from BASF. Other UV and light stabilizers are commercially available, LowLite from Chemtura, OnCap from PolyOne, and E. coli from Delaware, USA. I. Illustrated by the Light Stabilizer 210 from the duPont de Nemours and Company. For example, in order to minimize the possibility of migration of the anti-aging additive from the sealant or its cured product, an oligomer (high molecular weight) stabilizer is further added in the anti-aging additive or as an anti-aging additive. Available. Examples of such oligomeric antioxidant stabilizers include TINUVIN® 622, which is a dimethyl ester of butanedioic acid copolymerized with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol. Is done. Examples of heat stabilizers include iron oxide, carbon black, iron carboxylate, cerium hydrate, barium zirconate, cerium octanate and zirconium, porphyrins and the like, and combinations thereof.

The amount of anti-aging additive present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer, the intended use of the sealant, the curing conditions intended to expose the sealant, etc.). However, it can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises an amount of anti-aging additive 0-5, alternative 0.1-4, alternative 0.5-3% by weight, based on the total weight of the sealant.

In certain embodiments, the sealant comprises a water release agent, i.e., a component that releases water over time (eg, depending on application conditions such as temperature and / or pressure). Typically, the water release agent contains an amount of water sufficient to allow the sealant to partially and alternativeally completely react, and thus conditions applied over a sufficient period of time (eg, the operating temperature of the sealant). ) Is selected to release an amount of water when exposed to. However, in general, the water release agent is chosen to bind well with water, thereby preventing too much water from being released during the production and / or storage of the sealant. For example, the water release agent typically binds well to water during / during formulation of the sealant, and sufficient water is available for the condensation reaction of the (I) copolymer during or after the application process in which the sealant is used. To do so. This "controlled release" property can provide the benefit of preventing too much water from being released during the application process and / or water being released too quickly, which can be provided. This is because the reaction product formed by the condensation reaction of the (I) copolymer of the sealant can cause foaming or discharge. The particular water release agent selected will include various factors (eg, other components of the sealant, (I) amount / type of copolymer, (II) type of condensation reaction catalyst, process conditions in which the sealant will be incorporated. Etc.) and will be easily determined by those skilled in the art. Examples of suitable water release agents are exemplified by metal salt hydrates, hydrated molecular sieves, and precipitated carbonates. Specific examples include precipitated calcium carbonate available from Solvay under the WINNOFIL® SPM trademark. In certain embodiments, the water release agent is selected to be alternative, precipitated calcium carbonate, to include precipitated calcium carbonate. The water release agent can reliably choose not to release all water during formulation, and at the same time, when exposed to the applicable temperature range for a sufficient period of time, a sufficient amount of water for the condensation reaction of the (I) copolymer. Is released. The amount of water release agent present in the sealant depends on various factors (eg, (I) copolymer water permeability, vehicle / solvent presence / absence, desiccant presence / absence, method of blending / preparing the sealant, etc.). It depends on and can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises an amount of 1 to 50, 5 to 40 alternatives, 5 to 30 parts by weight of the water release agent, based on the total weight of all components in the sealant.

In some embodiments, the sealant comprises a pigment (ie, a component that supplies color to the sealant and / or its reaction product). Such pigments can include any inorganic compound, such as those of metals such as chromium oxide, titanium oxide, cobalt pigments, as well as those non-based on such metals, such as non-metallic inorganic compounds. Examples of suitable pigments include indigo, titanium dioxide, carbon black, and combinations thereof, as well as other commercially available pigments such as Tan-Tone 505P01 Green available from PolyOne. In certain embodiments, the pigment comprises carbon black. Specific examples of carbon black include Shawinigan Acetylene Black, which is commercially available from Chevron Phillips Chemical Company LP; SUPERJET® Carbon Black (eg, LB-1011), LB-1011, USA, Il Elementis Pigments Inc. SR 511 is sourced from Sid Richardson Carbon Co, Ohio, Akron, USA; and N330, N550, N762, N990 (from Degussa Engineered Carbons, Parsippany, USA). .. The amount of pigment present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer, the intended use of the sealant, the presence / absence of vehicle / solvent, etc.) and is readily available to those skilled in the art. It is determined. Generally, the sealant, if present, comprises an amount of more than 0-20, alternative 0.001-10, alternative 0.001-5% by weight, based on the total weight of the sealant.

In certain embodiments, the sealant comprises a rheology additive such as a rheology modifier and / or a viscosity modifier. Examples of suitable rheological additives include waxes; polyamides; polyamide waxes; cured castor oil derivatives; metal soaps such as calcium stearate, aluminum, and / or barium; and their derivatives, variants, and combinations. Is done. In certain embodiments, the rheology modifier is to facilitate filler uptake, sealant formulation, deaeration, and / or mixing (eg, during its preparation), as is well understood by those skilled in the art. Be selected. Specific examples of rheology additives include those known in the art that are commercially available. Examples of such rheological additives are Polyvest; commercially available from King Industries, Disparlon; commercially available from DuPont; Kevlar Fiber Pull, commercially available from Nanocor; Rheospan; Lubrizol, commercially available from Nanocor. Ircogel; Crayvallac® SLX commercially available from Palmer Holland, and combinations thereof.

In some embodiments, the rheology modifier comprises, as an alternative, a wax (eg, paraffin wax, microcrystalline wax, or a combination thereof). Waxes typically include non-polar hydrocarbons, which may include branched, cyclic, or combinations thereof. Examples of suitable waxes are SP96 (melting point 62-69 ° C), SP 18 (melting point 73-80 ° C), SP 19 (melting point 76-83 ° C), SP 26 (76-83 ° C). Melting point in the C range), SP 60 (melting point 79-85 ° C), SP 617 (melting point 88-93 ° C), SP 89 (melting point 90-95 ° C), and SP 624 (90-95 ° C). In the name of ° C melting point) Y, West Babylon's Strahl & Pitch, Inc. Includes petroleum polycrystalline wax available from. Further examples of suitable waxes include those sold under the trademark Multiwax® by the Crompton Corporation of Petrolia, USA. Such waxes include saturated branched and cyclic non-polar hydrocarbons and have a melting point of 79-87 ° C. Multiwax® 180-W; including saturated branched and cyclic non-polar hydrocarbons, 76-83. Includes Multiwax® W-445 with a melting point of ° C; Multiwax® W-835; containing saturated branched and cyclic non-polar hydrocarbons and having a melting point of 73-80 ° C. In certain embodiments, the wax optionally comprises a microcrystalline wax that is solid at room temperature (25 ° C.). In some embodiments, the wax is selected to have a melting point within the desired applicable temperature range (ie, the temperature range in which the sealant is intended to be used / applied). It is believed that the wax acts as a processing aid when melted and is substantially mitigated during the uptake of the filler in the composition being formulated, the formulation process itself, and the degassing step if used. For example, in certain embodiments, the wax has a melting temperature below 100 ° C., and even a simple static mixer is a partial (eg, a composition of multiple portions of the sealant) prior to application. If) mixing can be promoted. In such cases, the wax can also facilitate the application of the sealant with good rheology at a temperature of 80-110 ° C, optionally 90-100 ° C.

The amount of rheological additive present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer, the intended use of the sealant, the curing conditions intended to expose the sealant, the vehicle / solvent. It depends on the presence / absence, etc.) and can be easily determined by those skilled in the art. In general, the sealant, if present, comprises an amount of more than 0-20, alternative 1-15, and alternative 1-5 parts by weight of rheological additive based on the total weight of all components in the sealant. ..

In certain embodiments, the sealant comprises a vehicle (eg, a carrier vehicle such as a solvent and / or a diluent). As will be appreciated by those skilled in the art, the particular vehicle utilized will be the sealant or a portion thereof (eg, one or more portions of the sealant if the sealant is a composition of multiple portions). The introduction of certain components (eg, (I) copolymers, chain extenders, terminal blockers, etc.) has been selected to promote (eg, increase) the flow of the. Thus, suitable vehicles vary and generally include those that aid in the fluidization of one or more components of the sealant, but essentially do not react with any of such components. Therefore, the vehicle may be selected based on the solubility, volatility, or both of one or more components of the sealant. In this sense, solubility refers to a vehicle sufficient to dissolve and / or disperse one or more components of the sealant, and volatility refers to the vapor pressure of the vehicle. If the vehicle is too volatile (ie, has a vapor pressure that is too high for its intended use), air bubbles can form in the sealant at the applicable temperature, leading to cracks, and / or otherwise the sealant. It can weaken or have a detrimental effect on the properties of the cured product formed from. However, if the vehicle is not sufficiently volatile (ie, has a vapor pressure that is too low for its intended use), the vehicle may remain in the cured product of the sealant and / or act as a plasticizer for it. Can be done. Examples of suitable vehicles generally include silicone fluids, organic fluids, and combinations thereof.

In some embodiments, the sealant vehicle comprises or is a silicone fluid. Silicone fluids are usually low viscosity and / or volatile siloxanes. In some embodiments, the silicone fluid is a low viscosity organopolysiloxane, a volatile methylsiloxane, a volatile ethylsiloxane, a volatile methylethylsiloxane, or a combination thereof. Silicone fluids typically have viscosities in the range of 1 to 1,000 mm ² / sec at 25 ° C. In some embodiments, the silicone fluid comprises a silicone having the general formula (R ²⁸ R ²⁹ SiO) _I , each R ²⁸ and R ²⁹ being selected independently of H and a substituted or unsubstituted hydrocarbyl group. , The subscript I is 3-8. Specific examples of suitable silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetra. Decamethylhexasiloxane, hexademethylheptasiloxane, heptamethyl-3-{(trimethylsilyl) oxy)} trisiloxane, hexamethyl-3,3, bis {(trimethylsilyl) oxy} trisiloxanepentamethyl {(trimethylsilyl) oxy} cyclotri Siloxane, and polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylylmethicone, hexamethyldisiloxane, heptamethyloctyldisiloxane, hexyltrimethicone, etc., and derivatives thereof. Variants and combinations thereof are included. Additional examples of suitable silicone ^fluids, include polyorganosiloxanes suitable vapor pressure such as ^{5x10 -7 ~1.5x10 -6 m 2 / s} , DOWSIL; ( R) 200 Fluids and DOWSIL (registered Includes OS FLUIDS (trademark) and is commercially available from Dow Silicones Corporation of Mich, Midland, USA.

In certain embodiments, the vehicle of the sealant comprises an organic fluid or is an alternative organic fluid, typically an organic containing volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. Contains oil. Common examples of such organic _fluids, C 6 _{-C 16 alkanes,} C 8 _{-C 16} isoalkanes (e.g., isodecane, isododecane, etc. _{isohexadecane),} C 8 _{-C 16} Branched esters (e.g., neopentanoate Volatile hydrocarbon oils such as isohexyl, isodecyl neopentate, etc.), as well as derivatives, variants, and combinations thereof. Additional examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols with four or more carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, Includes aromatic halides, and combinations thereof. Hydrocarbons include isododecane, isohexadecane, Isopar L (C _11- C ₁₃ ), Isopar H (C _11- C ₁₂ ), and hydrogenated polydecene. Examples of ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3ethoxypropionate, propylene glycol methyl ether acetate, and tri. Pentacyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylic / dicaprylate, octyl ether, palmitic acid Includes octyl, and combinations thereof.

In some embodiments, the vehicle comprises or is an organic solvent. Organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and n-propanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; heptane, hexane, And aliphatic hydrocarbons such as octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, and ethylene glycol n-butyl ether; dichloromethane, 1, 1, Halogenized hydrocarbons such as 1-trichloroethane and methylene chloride; chloroform; dimethylsulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran; white spirit; mineral spirit; naphtha; n-methylpyrrolidone; and their derivatives, variants, and Those containing a combination thereof are included.

Other vehicles are more available in the sealant. For example, in some embodiments, the vehicle comprises or is an ionic liquid. Examples of ionic liquids include anion-cation combinations. Generally, anions are derived from alkyl sulphate anions, tosylate anions, sulfonate anions, bis (trifluoromethanesulfonyl) imide anions, bis (fluorosulfonyl) imide anions, hexafluorophosphate anions, tetrafluoroborate anions and the like. The cation is selected from an imidazolium-based cation, a pyrrolidinium-based cation, a pyridinium-based cation, a lithium cation, and the like. However, combinations of multiple cations and anions are also available. Specific examples of the ionic liquid are usually 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis- (trifluoromethanesulfonyl) imide, 3-. Methyl-1-propylpyridiniumbis (trifluoromethanesulfonyl) imide, N-butyl-3-methylpyridiniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyridiniumbis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (Trifluoromethanesulfonyl) imide, methyltrioctylammonium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1,2-dimethyl-3-propyl imidazolium bis (trifluo) Lomethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-vinyl imidazolium, bis (trifluoromethanesulfonyl) imide, 1-allyl imidazolium bis (trifluoromethanesulfonyl) imide, 1 -Allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imides, lithium bis (trifluoromethanesulfonyl) imides and the like, as well as derivatives, variants and combinations thereof.

The amount of vehicle present in the sealant depends on a variety of factors (eg, the amount and / or type of (I) copolymer, the mode in which the sealant is formulated, the curing conditions in which the sealant is intended to be exposed, etc.). , Can be easily determined by those skilled in the art. Generally, if present, the sealant comprises 1-99, alternative 1-75, alternative 2-60, alternative 2-50% by weight of vehicle based on the total weight of the sealant.

In certain embodiments, the sealant comprises a tackifier. Typical examples of suitable tackifiers are typically aliphatic hydrocarbon resins (eg, hydrogenated polyolefins with 6-20 carbon atoms), terpene hydride resins, rosin esters, hydrogenation. Includes rosin glycerol esters, or combinations thereof. Specific examples of suitable tackifiers include natural or modified rosins such as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydride rosin, dimerized rosin, and polymerized rosin; glycerol esters of light colored wood rosins, hydride rosins. Glycerol and pentaerythritol esters of natural or modified rosins such as glycerol esters of glycerol, glycerol esters of polymerized rosins, pentaerythritol esters of hydrocarbon rosins, and phenol-modified pentaerythritol esters of rosins; styrene / terpenes and / or alphamethylstyrene / terpenes. Copolymers of natural terpenes such as polymers and / or terpolymers; those produced by the polymerization of terpene hydrocarbons (eg, pinene) in the presence of Friedel-Crafts catalysts, and their hydrogenated products (eg, polyterpenes hydride). Polyterpene resins having a softening point of 60 to 150 ° C as measured by the ASTM method E28 such as; phenol-modified terpene resins such as those produced by acid-mediated condensation of bicyclic terpenes and phenols and their hydrocarbon derivatives; mainly Those produced through the polymerization of monomers composed of olefins and diolefins, those having a ring-shaped softening point at 60 to 135 ° C., and aliphatic petroleum hydrocarbon resins such as hydrided aliphatic petroleum hydrocarbon resins; Included are cyclic petroleum hydrocarbon resins and terpene derivatives thereof; aliphatic / aromatic or alicyclic / aromatic copolymers and terpene derivatives thereof; and combinations thereof. In some embodiments, the sealant comprises a solid tackifier (ie, a tackifier having a ring-shaped softening point above 25 ° C.). Other examples of suitable tackifiers are ESCOREZ 1102, 1304, 1310, 1315, and 5600 from Exxon Chemical, and the fats exemplified by Estotac H-100, H-115E, and H-130L from Estman. Group Hydrocarbon Resins; Terpene Hydrocarbon Resins Illustrated by Arkon P 100 from Arakawa Chemicals and Wingtack 95 from Goodyear; Staybelite Ester 10 from Hercules and Rozine Glycer Ester Hydride Illustrated by Foral; Polyterpenes exemplified by; aliphatic / aromatic and / or alicyclic / aromatic resins exemplified by ECR 149B and ECR 179A from Exxon Chemical; and a variety of commercially available combinations thereof. The amount of tackifier present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer, the type and / or amount of other components of the sealant, the intended use of the sealant, etc.). ) Depends on and can be easily determined by those skilled in the art. Generally, the sealant, if present, comprises 1 to 20 parts by weight of the tackifier based on the total weight of all components in the sealant.

In certain embodiments, the sealant comprises a corrosion inhibitor. Examples of suitable corrosion inhibitors include benzotriazoles, mercaptabenzotriazoles and the like, and combinations thereof. Specific examples of suitable corrosion inhibitors are known in the art and are CUVAN® 826 (eg, 2,5-dimercapto-1,3,4-thiadiazole derivatives), and CUVAN®. 484 (alkylthiadiazole) and the like are commercially available, and R. cerevisiae R.M. T. Available from Vanderbilt.

The amount of corrosion inhibitor present in the sealant depends on various factors (eg, the amount and / or type of (I) copolymer, the intended use of the sealant, the curing conditions intended to expose the sealant, etc.). , Can be easily determined by those skilled in the art. Generally, the sealant, if present, contains an amount of 0.05-0.5% by weight of the corrosion inhibitor based on the total weight of the sealant.

As introduced in the various paragraphs above, the various components of the sealant may be used for multiple purposes, and therefore certain additives may overlap with respect to the components described herein. For example, certain alkoxysilanes can be useful as fillers, adhesion promoters, and crosslinkers. In addition, the sealant may further contain additional additives not mentioned above, such as catalyst inhibitors, curing accelerators, discoloration additives and the like. Such additional additives are independently selected and each utilized in the sealant in an amount selected based on its intended use, as readily determined by those skilled in the art. Typically, if present, the sealant is added in an amount of 0.001-10, alternative 0.01-5, alternative 0.1-1% by weight, based on the total weight of the sealant. Contains each of the additives in.

As mentioned above, the sealant can be prepared as a partial composition or as a multipartial composition (including, for example, 2, 3, 4, or more moieties). For example, in some embodiments, the sealant is prepared as a partial composition and can be prepared by combining all the ingredients together by any convenient means such as mixing. Such partial compositions can be made by optionally combining (eg, premixing) the (I) copolymer with various additives (eg, fillers) to form an intermediate mixture, followed by intermediate. The mixture is combined with (II) a premix containing a condensation reaction catalyst and various other additives (eg, through mixing) to form a sealant mixture or sealant. Other additives (eg, anti-aging additives, pigments, etc.) may be added to the sealant at any desired step, such as in combination with an intermediate mixture, premix, or sealant mixture. Thus, a final mixing step can be performed (eg, under substantially anhydrous conditions) to form the sealant, which is usually substantially in a sealed container, eg, until ready for use. Stored under anhydrous conditions.

In some embodiments, the sealant is prepared as a multipartial composition (eg, when a cross-linking agent is utilized). In such embodiments, the (II) condensation reaction catalyst and cross-linking agent are usually stored in separate parts and combined immediately prior to use of the sealant. For example, the sealant is prepared by combining (I) a copolymer and a cross-linking agent to form a first (ie, curing agent) moiety by any convenient means (eg, mixing). May include a sex composition. The second (ie, base) moiety can be prepared by combining (II) a condensation reaction catalyst and (I) a copolymer by any convenient means (eg, mixing). The ingredients can be combined under ambient or anhydrous conditions at ambient or high temperatures, depending on various factors, for example, whether a partial or multipartial composition is selected. The base and hardener portions can then be combined by any convenient means, such as mixing, just prior to use. The base and hardener moieties may be combined in a ratio of 1: 1 or in a relative amount of base: hardener in the range of 1: 1-10: 1.

The equipment used to mix the components of the sealant is not particularly limited and usually depends on the type and amount of each component selected for use in the sealant or a portion thereof (collectively, the "sealant composition"). Is selected. For example, agitated batch kettles can be used for relatively low viscosity sealant compositions such as compositions that react to form rubbers or gels. Alternatively, continuous blending equipment (eg, extruders such as twin-screw extruders) can be used for more viscous sealant compositions and sealant compositions containing relatively large amounts of particles. Illustrative methods that can be used to prepare the sealant compositions described herein include, for example, the methods disclosed in US Patent Publication Nos. 2009/0291238 and 2008/0300358, wherein. Some are incorporated herein by reference.

The sealant composition produced as described above may be stable when stored in a container that reduces or prevents exposure of the sealant composition to moisture. However, the sealant composition can react via a condensation reaction when exposed to atmospheric moisture. In addition, when a water release agent is utilized, the sealant composition can react via a condensation reaction without exposure to atmospheric moisture.

Further cure products are provided. The cured product is formed from the sealant. More specifically, the cured product is formed by curing the sealant, for example via the condensation reaction described above.

Further provided are composite articles containing hardened products. More specifically, the composite article comprises a substrate and a cured product placed on the substrate. The composite article is formed by placing the sealant on a substrate and curing the sealant to feed the cured product onto the substrate, thereby preparing the composite article. Substrates are exemplified by, for example, external building façade.

Also disclosed is a method of sealing a space defined between two elements. The method involves applying the sealant to the space, curing the sealant in the space, thereby sealing the space.

As used herein, the terms "comprising" or "complying" are "inclusion", "include", "essentially consist of", and "consisting of". It is used in the broadest sense to mean and embrace the concept of ". The use of "for example", "eg (eg)", "etc.", and "contains" to enumerate exemplary examples is not limited to the enumerated examples. Thus, "eg" or "etc." means "eg, but not limited" or "etc. but not limited" and includes other similar or equivalent examples. As used herein, the term "about" helps to reasonably include or explain minor variations in numerical values measured by instrumental analysis or as a result of manipulating a sample. Such minor fluctuations are% of values on the order of ± 0-25, ± 0-10, ± 0-5, or ± 0-2.5. In addition, the term "about" applies to both numbers when associated with a range of values. In addition, the term "about" may apply to numbers even if not explicitly stated.

Generally, as used herein, a hyphen "-" or dash "-" in the range of values is "from" or "from"; ">" is "exceeded". Or "greater than"; "≥" is "at least" or "greater than or equal to"; "<" is "below" or "less than"; "≤" is "maximum" or "less than or equal to" ". On an individual basis, each of the above-mentioned patent applications, patents, and / or patent application publications is expressly incorporated by reference in its entirety into one or more non-limiting embodiments.

The scope of the appended claims is not limited to the expression of "forms for carrying out the invention" and the specific compounds, compositions, or methods described therein, and the scope of the appended claims is specified. Please understand that it can differ between embodiments of. Different from each member of each Markush group independent of all other Markush members, special and with respect to any Markush group relying herein to describe a particular feature or embodiment of various embodiments. / Or unexpected results may be obtained. Each member of the Markush Group may be relied upon individually or in combination to provide appropriate support for specific embodiments within the appended claims.

Moreover, any scope and subrange that relies on the description of the various embodiments of the invention is included independently and collectively within the scope of the appended claims, such values are herein. It is understood to explain and intend the entire range, including their whole and / or fractions, even if not explicitly stated. Those skilled in the art will appreciate that the listed ranges and subranges fully describe and validate various embodiments of the invention, and that such ranges and subranges are related half, one-third, one-quarter. It is easily recognized that it can be explained in more detail, such as one-fifth. As a mere example, the range of "0.1 to 0.9" is the lower third, or 0.1, 0.3, the middle third, or 0.4 to 0.6, and the upper three. It can be explained in more detail in one-third, ie 0.7-0.9, which is within the scope of the claims, individually and collectively attached, and can be individually and / or collectively relied upon and attached. Provide appropriate support for specific embodiments within the scope of the claims. Further, with respect to languages that define or modify ranges such as "at least", "greater than", "less than", "less than or equal to", it should be understood that such languages include subranges and / or upper or lower limits. .. As another example, the range "at least 10" essentially includes at least 10-35 subranges, at least 10-25 subranges, 25-35 subranges, etc., and each subrange is individual. And / or may be collectively relied upon to provide appropriate support for a particular embodiment of the appended claims. Finally, the individual numbers within the disclosed scope can be relied upon to provide appropriate support for the particular embodiment of the appended claims. For example, the range "1-9" includes various individual integers such as 3 as well as individual numbers including decimal points (or decimals) such as 4.1, which can be relied upon and attached. Provide appropriate support for specific embodiments within the scope of the claims.

The following examples are intended to illustrate the invention and should by no means be considered as limiting the scope of the invention. Table 1 below shows the abbreviations used in the examples.

Preparation Example 1:
A dry four-necked flask was placed in a temperature controlled heating block and fitted with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. The flask was purged with N _2, it was placed polyether compound therein. The flask was heated and held for 2 hours 105 ° C. under vacuum with intermittent N ₂ purge. The flask was then cooled to 85 ° C. A hydrosilylation catalyst was added (5 ppm, 1 wt% solution of 0-0719 dissolved in MM). The chain-extending organic silicone compound was added in droplets. Adiabatic exotherm is observed with an increase in temperature of 5-10 ° C. and the reaction temperature is maintained at about 95 ° C. by adjusting the addition of chain-extending organic silicone compounds accordingly. The reaction temperature is maintained for a time of about 95 ° C. (T1) until the reaction is considered complete, i.e. until SiH is no longer detected by ¹ H NMR or FTIR. The end-protected organic silicone compound was added in droplets. Adiabatic heat generation was observed with an increase in temperature of about 5 ° C. The reaction was then heated to about 95 ° C. to completion and kept for a period of time (T2), with additional end-protected organic silicone compounds added if C = C was excessive as observed by 1 H NMR. The reaction was considered complete when either C = C was absent or less than 2% of the starting amount (according to ^{1 1} H NMR). If all C = C was consumed but residual SiH was still present (by ^{1 1} H NMR or FTIR), it was added in excess of ATMS to remove residual SiH. When complete, the reaction mixture was heated and kept at 105 ° C. for 2 hours under vacuum to remove all volatiles. The contents of the flask are then cooled to room temperature and sealed in a Nalgene vessel under N ₂ flow. The finished material was referred to as a silicone polyether copolymer.

Examples 1-4
Silicone polyether copolymers were prepared according to the procedure shown in Preparation Example 1. Table 2 below shows the relative amounts of the polyether compound, the chain extended organic silicone compound (CEOC), and the end protected organic silicone compound (EOC).

In the structure given to the example silicone polyether copolymers in Table 2 below, Y represents the polyether moiety formed from the polyether compound; Z represents the siloxane moiety formed from the chain-extended organic silicone compound. Representation; X represents the silicone moiety formed from the end-protected organic silicone compound; c is the approximate number of terminal functional groups X of the silicone polyether copolymer.

Preparation Example 2: Two-Step Synthesis Procedure for Preparing Silicone Polyether Copolymer A dry four-necked flask is placed in a temperature-controlled heating block, mechanical stirrer, thermometer, dropping funnel, and reflux condenser. Was installed. The flask was purged with N _2, it was placed polyether compound therein. The flask was heated and held for 2 hours 105 ° C. under vacuum with intermittent N ₂ purge. The flask was then cooled to 85 ° C. The end-protected organic silicone compound is loaded onto the reaction flask. A hydrosilylation catalyst was added (5 ppm, 1 wt% solution of 0-0719 dissolved in MM). Adiabatic heat generation was observed with an increase in temperature of 5-10 ° C. The reaction temperature is maintained for a time of about 95 ° C. (T1) until the reaction is considered complete, i.e. until SiH is no longer detected by ¹ H NMR or FTIR. The chain-extending organic silicone compound was added in droplets. Adiabatic exotherm is observed with an increase in temperature of 5-10 ° C. and the reaction temperature is maintained at about 95 ° C. by adjusting the addition of chain-extending organic silicone compounds accordingly. The reaction was then heated to about 95 ° C. to completion and kept for a period of time (T2), with additional end-protected organic silicone compounds added if C = C was excessive as observed by 1 H NMR. The reaction was considered complete when either C = C was absent or less than 2% of the starting amount (according to ^{1 1} H NMR). If all C = C was consumed but residual SiH was still present (by ^{1 1} H NMR or FTIR), it was added in excess of ATMS to remove residual SiH. When complete, the reaction mixture was heated and kept at 105 ° C. for 2 hours under vacuum to remove all volatiles. The contents of the flask are then cooled to room temperature and sealed in a Nalgene vessel under N ₂ flow. The finished material was referred to as a silicone polyether copolymer.

Examples 5-7
Silicone polyether copolymers were prepared according to the procedure shown in Preparation Example 2. Table 3 below shows the relative amounts of the polyether compound, the chain extended organic silicone compound (CEOC), and the end protected organic silicone compound (EOC).

In the structure given to the example silicone polyether copolymers in Table 3 below, Y represents the polyether moiety formed from the polyether compound; Z represents the siloxane moiety formed from the chain-extended organic silicone compound. Representation; X represents the silicone moiety formed from the end-protected organic silicone compound; c is the approximate number of terminal functional groups X of the silicone polyether copolymer.

Preparation Example 3: One-Step Procedure for Preparing Silicone Polyether Copolymer A dry four-necked flask is placed in a temperature-controlled heating block and equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. I installed it. The flask was purged with N _2, it was placed polyether compound therein. The flask was heated and held for 2 hours 105 ° C. under vacuum with intermittent N ₂ purge. The flask was then cooled to 85 ° C. The chain-extending organic silicone compound and the end-protected organic silicone compound are then loaded onto the flask. A hydrosilylation catalyst was added (5 ppm, 1 wt% solution of 0-0719 dissolved in MM) and adiabatic exotherm was observed with an increase in temperature of 5-10 ° C. The reaction is then heated to about 95 ° C. for a period of time (T1) until the reaction is complete, that is, until either ¹ H NMR eliminates C = C or is less than 2% of the starting amount. ). If C = C remained, an additional end-protected organic silicone compound was added. If all C = C was consumed but residual SiH was still present (by ^{1 1} H NMR or FTIR), it was added in excess of ATMS to remove residual SiH. When complete, the reaction mixture was heated and kept at 105 ° C. for 2 hours under vacuum to remove all volatiles. The contents of the flask are then cooled to room temperature and sealed in a Nalgene vessel under N ₂ flow. The finished material was referred to as a silicone polyether copolymer.

Example 8
Silicone polyether copolymers were prepared according to the procedure shown in Preparation Example 3. Table 4 below shows the relative amounts of the polyether compound, the chain extended organic silicone compound (CEOC), and the end protected organic silicone compound (EOC) used in this example.

In the structure given to the silicone polyether copolymer of Example 10 in Table 4 below, Y represents the polyether moiety formed from the polyether compound; Z represents the siloxane moiety formed from the chain-extended organic silicone compound. Represents; X represents the silicone moiety formed from the end protected organic silicone compound; c is the approximate number of end functional groups X of the silicone polyether copolymer.

The viscosities, molecular weights (GPCs), molecular weights (GPCs), and polydispersity (PDs) of the silicone polyether copolymers of Examples 1-8 were obtained and calculated and are shown in Table 5 below.

Examples 1-8: Curing and Testing Procedures for Silicone Polyether Copolymers of Examples 1-8 30 g samples of each of the Silicone Polyether Copolymers of Examples 1-8 are 0 in a 40 g capacity polypropylene mixing cup for a Blacktek speed mixer. It was mixed with .03 g of dibutyltin dilaurate and mixed at 2000 rpm for 1 minute. The mixture was placed on a Teflon plate with an edge guard measuring 10 cm x 10 cm. The Teflon plate was placed in a room controlled to a humidity of 50% and a temperature of 23 ° C. The plates were left in the room for 7 days to cure, then transferred to an air circulation oven set to 50 ° C. where the moisture content in the air was not adjusted and kept in the oven for 4 days. Finally, the sample was removed from the oven and cooled to room temperature. Dogbone specimens were cut from the sample with a carbon steel die for tensile testing and small pieces were cut from the sample for differential scanning calorimetry (DSC).

The dogbone sample size for the tensile test is 50 mm long with a narrow neck length of 20 mm. An MTS test frame with a 100 N full capacity load cell was used for the test. The test speed is 50.8 cm / min. The strain was calculated as the displacement over the length of the narrow neck. The stress at rupture was calculated by dividing the peak stress by the initial cross-sectional area of the narrow neck region.

Differential scanning calorimetry (DSC) was performed with the TA Instrument Discovery Series DSC2500. The sample was weighed into a Tzero aluminum dish (about 10 mg sample) and analyzed instrumentally, the temperature was first lowered to −180 ° C. at 10 ° C./min and then raised to 200 ° C. at 10 ° C./min. The heat required to accommodate the ramping process was recorded and Tg was detected as a sudden change in heat capacity. The properties measured from these silicone-polyether copolymers are included in Table 6.

Preparation Example 4: Sealant Preparation Procedure A premixed solution of aminoethylaminopropyltrimethoxysilane (as an adhesion promoter) and dibutyltin dilaurate (as a catalyst) was combined in an ounce glass vial. The solution was then mixed by hand until a clear pale yellow color was obtained and the mixture was set aside for use in later compounding processes.

Up to 300 long mixing jars designed for use with the DAC 600.2 VAC SpeedMixer were placed on the balance and tare. Silicone polyether copolymers, diisononylphthalate (as a plasticizer), and vinyltrimethoxysilane (as a desiccant) were placed in jars. The contents of the jar were mixed at 800 rpm for 30 seconds. Precipitated calcium carbonate (Specialty Minerals, UltraPflex from Inc) was added to the jar, the jar was placed in the mixer and mixed at 1300 rpm for 30 seconds. The jar was removed from the mixer and manually scraped off with a spatula to remove all calcium carbonate remaining on the jar wall and returned to the mixer for another 30 second mixing cycle at 1500 rpm. The jar was placed on a balance and ground calcium carbonate (CS-11 from Solvay Carbonates) was placed therein. The jar was returned to the mixer at 1300 rpm for 30 seconds, scraped off by hand and then mixed at 2000 rpm for another 30 seconds. The mixture formed above was weighed into a jar, mixed at 1300 rpm for 30 seconds, and then scraped off by hand. The final step of degassing the material was performed. The lid of the solid mixing jar was replaced with a perforated one to allow air to escape from the mixing jar when in the mixing / vacuum chamber. The program was continuously mixed and run according to the following set points: mixing at 800 rpm at 3.5 psi vacuum pressure for 37 seconds, mixing at 1200 rpm with a 3.5 psi vacuum for 40 seconds, at 800 rpm for 35 seconds. Mix and evacuate to ambient conditions. The resulting sealant was encapsulated in a 6 ounce SEMCO tube and set aside for later testing.

Table 7 below shows the components used in the sealant preparation procedure of Preparation Example 4 and their relative amounts.

Example 9
The sealant was prepared according to the sealant preparation procedure of Example 12 using the silicone polyether copolymer of Example 3.

Example 10
Sealants were prepared according to the sealant preparation procedure of Example 12 using the silicone polyether copolymer of Example 4.

Example 11
Sealants were prepared according to the sealant preparation procedure of Example 12 using the silicone polyether copolymer of Example 5.

Example 13: Sealant Properties The physical and curing properties of Examples 9-11 were evaluated according to their respective procedures below.

Tuck Free Time: A 100 mil thick slab of a particular sealant was pulled down onto a piece of polyethylene terephthalate (PET). A small strip of PET was then lightly pressed against the surface of a particular sealant to check for hardening. If the sealant did not transfer to the PET strip, the sealant was considered non-sticky.

Extrusion rate: SEMCO Nozzle Type 440 was attached to a 6 ounce SEMCO tube. A brief extrusion was performed to fill the extrusion nozzle. Three data points were collected for 3 seconds each with a 90 psi push output. The extrusion rate was then calculated in grams per minute as the average of the three data points.

The particular sealant was cured at a relative humidity of 50% and 23 ° C. for 7 days. The durometer was measured by ASTM Method D2240, Type A. Tension, elongation, and modulus were measured by ASTM Method D412. Table 8 below shows the physical properties of Examples 9-11.

Although the present invention has been described exemplary, it should be understood that the term used is intended to be the nature of the term described, not the limitation. Obviously, many modifications and modifications of the present invention are possible in the light of the above teachings. The present invention can be carried out by methods other than those specifically described.

Claims (25)

Silicone polyether copolymers having the formula X _g [Z _{j Yo} ] _c , each X being an independent silicone moiety having one of the formulas (I) or (II).
Each Y is an independently selected polyether moiety, and each Z is an independently selected siloxane moiety having the formula [R ¹ _h SiO _{(4-h) / 2} ] _d .
In the formula, each R ¹ is an independently selected substituted or unsubstituted hydrocarbyl group having 1 to 18 carbon atoms and each R ² is independently selected having 1 to 18 carbon atoms. Subscripts to be substituted or unsubstituted hydrocarbyl groups, each D ¹ is an independently selected divalent hydrocarbon group having 2 to 18 carbon atoms, and each subscript a is independently. 0 or 1, each subscript b is independently 0 or 1, subscript c is 1-150, each subscript d is 1-1000, each subscript Each subscript f is independently 0 or 1 under the condition that the letter e is independently 1 or 2 and f is 1 in each X and b is 1. The subscript g is> 1, the subscript h is independently selected from 0 to 2 in each portion indicated by the subscript d, and each subscript j is independently> 0 and <. 2 and each subscript o is independently> 0 and <2, and the subscript t is ≧ 0, provided that each part indicated by the subscript c has j + o = 2. Yes, the subscript u is> 0, silicone polyether copolymer. The silicone-polyether copolymer has the following formula
The silicone-polyether copolymer of claim 1, wherein in the formula, each X, Y, R ¹ , subscript c, and subscript d are defined above. (I) Each polyether moiety Y contains a polyether group having the formula −O− (C _n H _2n O) _w −, in which the subscript n is in each moiety represented by the subscript w. Selected independently from 2-4, the subscript w is 1-1000, (ii) each polyether moiety Y has a number average molecular weight of at least about 100, or (iii) at least one. The silicone polyether copolymer according to claim 1 or 2, wherein the polyether portion Y of the above is a polyhydroxyl polyether or a combination of (vi) (i)-(iii). Each polyether portion Y has the following equation
−CH ₂ −CH (R ³ ) − [D ² ] _{m −} O − [C ₂ H ₄ O] _x [C ₃ H ₆ O] _y [C ₄ H ₈ O] _z − [D ² ] _m −CH (R ³ ) -CH _2- ,
In the formula, each R ³ is an independent hydrocarbyl group, alkoxy group, silyl group, or H having 1 to 6 carbon atoms, and each D ² is an independent hydrocarbyl group having 1 to 6 carbon atoms. It is a divalent group to be selected, the subscript m is 0 or 1, the subscript x is 0-999, the subscript y is 1-1000, and the subscript z. Is 0-999, and the unit represented by the subscripts x, y, and z can be in randomized or block form in the polyether portion Y, any one of claims 1-3. The silicone-polyether copolymer described in. (I) Each R ³ is methyl, (ii) each subscript m is 1, and each D ² is CH ₂ , or (iii) (i) and (ii). The silicone-polyether copolymer according to claim 4, which is both of the above. (I) Is each R ¹ methyl, (ii) each R ² is propyl, (iii) each subscript a is 0, (iv) each D ¹ is C ₂ or H is _4, or any combination of (v) (i) ~ ( iv), the silicone polyether copolymer according to any one of claims 1 to 5. A method for preparing a silicone polyether copolymer, wherein the method is
In the presence of a hydrosilylation catalyst, a polyether compound having two or more terminal unsaturated groups on average, a chain-extending organic silicone compound, and a terminal-protected organic silicone compound are reacted to obtain the silicone polyether copolymer. Including that
The method, wherein the silicone polyether copolymer is the silicone polyether copolymer according to any one of claims 1 to 6. The polyether compound has the following formula and
Y ¹ [R ⁴ ] _i ,
In the formula, each R ⁴ is an independently selected unsaturated group having 2 to 14 carbon atoms, the subscript i is> 1, and Y ¹ is the formula −O− (C). _n H _2n O) A independently selected polyether moiety containing a polyether group with _w −, with the subscript n selected independently from 2-4 in each moiety indicated by the subscript w. The method according to claim 7, wherein the subscript w is 1 to 1000. In the polyether compound
(I) The polyether portion Y ¹ has the following formula.
-O- [C ₂ H ₄ O] _x [C ₃ H ₆ O] _y [C ₄ H ₈ O] _z- ,
In the formula, each subscript x is 0 to 999, each subscript y is independently 1 to 1000, and each subscript z is independently 0 to 999, subscript. letters x, y, and units represented by z, or may be a randomized or block form in the polyether moiety Y ^1,
(Ii) Each R ⁴ has the following equation
CH ₂ C (R ³ )-[D ² ] _m- ,
In the formula, each R ³ is an independent hydrocarbyl group, alkoxy group, silyl group, or H having 1 to 6 carbon atoms, and each D ² is an independent hydrocarbyl group having 1 to 6 carbon atoms. The method of claim 8, wherein the divalent group selected and the subscript m is 0 or 1, or both (iii) (i) and (ii). Formula ^{_{CH 2 C (R 3) -}} [D 2] m - each ^{R 4} of the (i) each ^{R 3,} or a methyl, (ii) the subscript m each under a 1, and the The method of claim 9, wherein D ² is CH ₂ or both (iii) (i) and (ii). The chain-extended organic silicone compound is (i) a linear hydrogenated silicone functional organic silicone compound, (ii) a branched hydrogenated silicone functional organic silicone compound, or (iii) (i) and (ii). The method according to any one of claims 7 to 10, which comprises both of ii). The chain-extended organic silicone compound contains the linear hydrogenated silicone functional organic silicone compound, and the linear hydrogenated silicone functional organic silicone compound has the following formula.
11. In the formula, each R ¹ is an independently selected substituted or unsubstituted hydrocarbyl group having ¹ to 18 carbon atoms, and each subscript d'is 1 to 999. The method described. The end-protected organic silicone compound has formula (III) or (IV) and
In the equation, each R ¹ , R ² , D ¹ , subscript a, subscript b, subscript e, subscript f, subscript t, and subscript u are defined above. The method according to any one of claims 7 to 12, which is as described above. (I) The polyether compound and the chain-extending organic silicone compound are reacted in the presence of the hydrosilylation catalyst to obtain a chain-extending silicone polyether compound, and the chain-extending silicone is obtained in the presence of the hydrosilylation catalyst. The polyether compound and the terminal-protected organic silicone compound are reacted to obtain the silicone polyether copolymer, or
(Ii) The polyether compound and the terminal-protected organic silicone compound are reacted in the presence of the hydrosilylation catalyst to obtain a terminal-protected silicone polyether compound, and the terminal protection is obtained in the presence of the hydrosilylation catalyst. Any of claims 7-13, wherein the silicone polyether compound and the chain-extending organic silicone compound are reacted to obtain the silicone polyether copolymer, or both (iii), (i) and (ii) are included. The method described in paragraph 1. (I) The chain-extending silicone polyether compound comprises reacting the polyether compound with the chain-extending organic silicone compound in the presence of the hydrosilylation catalyst to obtain the chain-extending silicone polyether compound. , Has the following formula,
In the formula, each R ⁴ is an independently selected unsaturated group having 2 to 14 carbon atoms, the subscript c is 1-150, and each subscript d is 1 to 1. 1000, where each Y ¹ is an independently selected polyether moiety containing a polyether group having the formula −O− (C _n H _2n O) _w −, where the subscript n is the subscript. The method of claim 14, wherein each portion represented by w is independently selected from 2-4 and the subscript w is 1-1000. In the chain extension silicone polyether compound,
(I) Each polyether portion Y ¹ has the following formula.
-O- [C ₂ H ₄ O] _x [C ₃ H ₆ O] _y [C ₄ H ₈ O] _z- ,
In the formula, each subscript x is 0 to 999, each subscript y is independently 1 to 1000, and each subscript z is independently 0 to 999, subscript. letters x, y, and units represented by z, or may be a randomized or block form in the polyether moiety Y ^1,
(Ii) Each R ⁴ has the following equation
CH ₂ C (R ³ )-[D ² ] _m- ,
In the formula, each R ³ is an independent hydrocarbyl group, alkoxy group, silyl group, or H having 1 to 6 carbon atoms, and each D ² is an independent hydrocarbyl group having 1 to 6 carbon atoms. 15. The method of claim 15, which is the divalent group of choice, wherein the subscript m is 0 or 1, or comprises both (iii) (i) and (ii). Formula ^{_{CH 2 C (R 3) -}} [D 2] m - each ^{R 4} of the (i) each ^{R 3,} or a methyl, (ii) the subscript m each under a 1, and the 16. The method of claim 16, wherein D ² is CH ₂ or both (iii) (i) and (ii). A silicone polyether copolymer prepared according to the method according to any one of claims 7 to 17. It ’s a sealant,
Silicone polyether copolymer and
Condensation reaction catalyst, including
A sealant, wherein the silicone polyether copolymer is the silicone polyether copolymer according to any one of claims 1 to 5, and 15. (I) Filler; (ii) Filling agent; (iii) Crosslinker; (iv) Surface modifier; (v) Drying agent; (vi) Bulking agent; (vii) Rheological agent; Fuels; (ix) plasticizers; (x) terminal blockers; (xxi) adhesives (xii) anti-aging additives; (xxii) water release agents; (xiv) pigments; (xv) rheology modifiers; (xvi) Carrier; (xxii) tackifier; (xxii) corrosion inhibitor; (xxix) catalyst inhibitor; (xx) adhesion accelerator; (xxii) viscosity modifier; (xxiii) UV absorber; (xxiii) antioxidant The sealant according to claim 19, further comprising a (xxiv) light stabilizer; or a combination of (xxv) (i)-(xxiv). The sealant according to claim 20, wherein the sealant comprises the filler, the cross-linking agent, the bulking agent, the plasticizer, and the adhesion promoter. The cured product of the sealant according to any one of claims 19 to 21. A composite article comprising a substrate and the cured product of claim 22 placed on the substrate. A method for preparing a composite article, wherein the method
Placing the sealant on the substrate and
Including curing the sealant to obtain a cured product on the substrate, thereby forming the composite article.
The method, wherein the sealant is the sealant according to any one of claims 19-21. A method of sealing a space defined between two elements.
Applying a sealant to the space and
Including curing the sealant in the space and thereby sealing the space.
The method, wherein the sealant is the sealant according to any one of claims 19-21.